JP2015522046A - Cosmetic composition containing shielding composite particles - Google Patents

Abstract

The subject of the present invention is a cosmetically acceptable medium in which a) at least one aqueous phase, b) an average particle size of between 0.1 and 30 μm, at least one particulate UV screening agent and at least one Composite particles A in spherical form, including a core composed of a kind of inorganic material and / or at least one kind of organic material, c) at least a single particle B of an inorganic UV screening agent having an average basic particle size of more than 0.07 μm It is a composition to contain.

Description

The subject of the present invention is a cosmetically acceptable medium,
a) at least one aqueous phase,
b) A spherical form having an average particle size between 0.1 and 30 μm, comprising a core composed of at least one particulate UV screening agent and at least one inorganic material and / or at least one organic material Composite particles A,
c) Single particle B of inorganic UV screening agent with average basic particle size greater than 0.07μm
It is a composition containing at least.

  This composition is intended for topical use and is specifically intended to photoprotect the skin and / or hair from ultraviolet (UV) radiation.

  Light irradiation between wavelengths 280nm and 400nm tans the human epidermis, especially the light between wavelengths 280nm and 320nm, known as UV-B rays, can harm skin burns and the progression of natural tanning It is known to cause erythema.

  For these reasons, and for aesthetic reasons, there is a certain demand for a method to control this natural sunburn and thereby control the color of the skin, so this UV-B radiation should be cut off. It is.

  UV-A rays that have a wavelength of 320-400 nm and cause sunburn of the skin are also known to be prone to inducing harmful changes to the skin, especially sensitive skin or skin that is continuously exposed to solar radiation. . In particular, UV-A rays cause loss of skin elasticity and appearance of wrinkles, leading to premature skin aging.

  Therefore, for aesthetic and cosmetic reasons, for example, to protect the natural elasticity of the skin, it is increasingly desirable to control the effects of UV-A rays on the skin. Therefore, it is also desirable to block UV-A irradiation.

  In order to protect skin and keratin materials from UV radiation, sunscreen compositions containing organic screening agents active within the UV-A and UV-B ranges are commonly used.

There are many cosmetics containing one or more inorganic and / or organic UV screening agents. Inorganic fine particles based on metal oxides such as titanium dioxide (TiO ₂ ) are usually intended for children's skin or sensitive skin and are used to protect the skin from UV rays.

  The metal oxide fine particles generally have an average basic particle size of 0.1 μm or less, preferably between 0.005 and 0.1 μm, preferably between 0.01 and 0.1 μm, preferentially between 0.015 and 0.05 μm. .

  Inorganic shielding agents such as metal oxide particles, especially titanium oxide particles with an average primary particle size of over 0.07 μm on average, can be used because high levels of protection can be obtained by combining them with organic UV shielding agents Has been. However, this particulate inorganic screening agent has the disadvantage of reducing the cosmetic quality of the cosmetic composition by producing a white film on the skin during application.

  The FR2882371, WO2006 / 083326 and WO98 / 37964 applications describe various methods for producing composite particles composed of materials comprising metal oxide nanoparticles such as titanium dioxide.

  Application WO2006 / 061835 describes a composition comprising a spherical composite based on a metal oxide and a hydrophobic polymer.

  Known in the cosmetics field is application EP1388550 and application WO98 / 22539, which uses composite particles comprising a core formed from a metal oxide coated with a silicone or a fluoro compound and a photoprotective cosmetic. Application WO98 / 22539, intended for its use as a composition, describes sunscreens containing silicon particles and / or particles of another solid compound in which the silicon is in stoichiometric excess. The particles have an average diameter of less than 0.12 μm and are coated with an oxide layer in the range of 0.001 to 0.3 μm in thickness.

Composite spherical particles with an average particle size of 2-7 μm, sunscreen formulations that can contain TiO ₂ encapsulated in spherical silica particles as a shielding system, such as those sold under the name Eospoly TR by Creations Couleurs Alternatively, a product sold by Sunjin Chemical under the name Sunsil T50 is known.

  These shielding materials have the disadvantage that they have a better cosmetic quality but still result in formulations that are still insufficiently effective.

FR2882371 WO2006 / 083326 WO98 / 37964 WO2006 / 061835 EP1388550 WO98 / 22539 WO95 / 22959 WO97 / 03643 GB2286774 EP743309 WO98 / 22447 GB2319523 EP-A-0790243 WO98 / 25922 FR2861075 US5687521 US5373037 US5362881 US5237071 US5166355 GB-A-2303549 DE19726184 EP-A-893119 US5888481 DE676103 CH350763 US5501850 US5961960 EP0669323 US5518713 US2463264 EP0921126 EP0712855 JP04134042 JP04134043 EP0576974 FR2395023 JP01158090 EP0390683 JP04134041 FR2506156 EP0693471 EP2528420 FR2529887 EP0694521 FR2638354 EP0714880 JP04290882 FR-A2639347 EP-A-893119 JP-87166517 WO93 / 10753 WO93 / 11095 WO95 / 05150 GB-A-2 303 549 EP-A-893119 EP1353642 WO2007 / 068371 WO2008 / 155059 WO-A-92 / 06778 EP1069142 FR2315991 FR2416008 US4077441 US4850517

Cosmetics & Toiletries, February 1990, 105, 53-64 J. Am. Chem. Soc., 79, 5706-5708, 1957 J. Am. Chem. Soc., 82, 609-611, 1960 J. Chem. Phys., 64, 1602 (1967) E. Mariani et al., 16th IFSCC Congress, New York (1990) Published by The Cosmetic, Toiletries and Fragrance Association, "International Cosmetic Ingredient Dictionary and Handbook", 1997, pages 371-386 and 524-528 Bangham, Standish and Watkins, J. Mol. Biol., 13, 238 (1965) J. Soc. Cosm. Chem. 1954 (5), 249-256 "HLB Index", McCutcheon's Emulsifiers & Detergents, 1998 International Edition, MC Publishing Company B.L.Diffey, J. Soc. Cosmet.Chem. 40, 127-133, (1989)

  Accordingly, there remains a need for anti-UV sun protection compositions based on inorganic UV screening agents that provide more effective photoprotection and do not have the above disadvantages.

  Surprisingly, advantageously, the inventors have shown that this need can be met by the composition according to the invention.

The first subject of the invention is in a cosmetically acceptable medium,
a) at least one aqueous phase,
b) A spherical form having an average particle size between 0.1 and 30 μm, comprising a core composed of at least one particulate UV screening agent and at least one inorganic material and / or at least one organic material Composite particles A,
c) Single particle B of inorganic UV screening agent with average basic particle size greater than 0.070μm
It relates to the composition containing at least.

  The composition according to the invention is effective for photoprotection.

  The following description and examples represent other advantages, aspects and properties of the invention.

Definitions The following definitions are used herein.

  The composition according to the present invention is a photoprotective composition intended to block UV radiation, and the photoprotective composition is also known as a sun protection composition or a sun protection composition.

  The phrase `` cosmetically acceptable '' has any unacceptable discomfort (stimulation, stiffness or redness) that has a favorable color, scent and feel and is likely to discourage consumers from using the composition. Without compatibility with the skin and / or its appendages or mucous membranes.

  The phrase “average particle size” is understood to mean the parameter D [4,3] measured using a “Mastersizer 2000” particle size analyzer (Malvern). The light intensity scattered by the particles according to the angle of illumination is converted into a particle size distribution according to Mie theory. The parameter D [4,3] is measured, which is the average diameter of a sphere with the same volume as the particle. For spherical particles, the “average diameter” is often referred to.

  The phrase “average basic particle size” means the particle size of particles that are not agglomerated.

  The phrase “free particles B” means that the particles B present in the composition are not incorporated in the matrix of composite particles A and / or on the surface of the matrix.

  The phrase “particulate organic UV screening agent” is (1) in the form of particles that are solid at 25 ° C. and insoluble in the cosmetically acceptable medium of the composition of the present invention; Optional, which makes it possible to prevent or at least limit this irradiation from coming into contact with human keratinous substances by means of UVA and / or UVB absorption and / or reflection and / or scattering via known mechanisms Means organic molecules.

  The phrase “human keratinous substance” means skin (body, face, area around eyes), hair, eyelashes, eyebrows, body hair, nails, lips or mucous membranes.

Shielding composite particle A
The spherical composite particles A used according to the invention preferably have an average particle size of between 0.1 and 30 μm, preferably between 0.1 and 20 μm, even more preferentially between 0.1 and 10 μm.

  The spherical particles A used according to the invention comprise a core composed of at least one particulate UV screening agent and at least one inorganic material and / or at least one organic material.

  According to a first variant, the composite particles A contain a core comprising at least one organic material and / or at least one inorganic material containing particles of particulate UV screening agent. According to this embodiment, the matrix indicates inclusions, and the particulate UV screening agent particles are encased in the inclusions of the matrix.

  According to a second variant, the spherical composite particles A are organic and / or inorganic materials that are coated with at least one layer of particulate UV screening agent that may be bound to the matrix using a binder. Contains the created core.

  According to a third variant, the composite particles A contain a particulate UV screening agent coated with at least one layer of organic material and / or inorganic material.

  The core may also be formed from one or more organic and / or inorganic materials. In that case, this is the absence of a continuous phase of a material such as an alloy, i.e. a continuous phase in which the material can no longer dissociate, or a material composed of an organic or inorganic material, for example coated with another different organic or inorganic material layer It may be a continuous phase.

  The mass content of the particulate UV screening agent in the composite particles A according to the invention is preferably between 1% and 90%, preferably between 2% and 80%, better still between 3% and 70%. It is.

  According to one variant, the composite particles are in particular biodegradable or biocompatible materials, fatty substances, e.g. surfactants, especially when the composite particles A comprise a matrix coated with a layer of particulate UV screening agent It may be further coated with an additional coating selected from agents or emulsifiers, polymers and oxides.

  The shielding composite particle A has a spherical shape.

  The term “spherical” means that the sphericity index of a particle, ie the ratio between its maximum diameter and its minimum diameter, is less than 1.2.

  Preferably, the content of composite particles A in the composition according to the invention is 1% to 70% by weight, preferably 1.5% to 50% by weight, preferably 2% by weight, relative to the total weight of the cosmetic composition. To 40% by weight.

  The inorganic material that can be used in the core of the spherical composite particles A according to the invention can be selected from the group formed from glass, silica and aluminum oxide, and mixtures thereof.

  Organic materials that can be used to form the core of spherical composite particles A are poly (meth) acrylate, polyamide, silicone, polyurethane, polyethylene, polypropylene, polystyrene, polycaprolactam, polysaccharide, polytetrafluoroethylene, polypeptide, polyvinyl derivative , Waxes, polyesters, and polyethers, and mixtures thereof.

Preferably, the matrix of spherical composite particles A is
-SiO ₂ ,
-Poly (methyl methacrylate),
-Copolymers of styrene and C1 / C5 alkyl (meth) acrylate derivatives,
-Polyamides such as Nylon (registered trademark),
-Containing a material or material mixture selected from polytetrafluoroethylene.

  Composite particles A in spherical form are characterized by an average diameter between 0.1 and 30 μm, preferably between 0.1 and 20 μm, more preferably between 0.1 and 10 μm.

Particulate UV Screening Agent The particulate UV screening agent according to the present invention is selected from particulate organic UV screening agents and inorganic screening agents.

Inorganic screening agents Inorganic UV screening agents are generally from metal oxides, preferably titanium oxide, zinc oxide or iron oxide, or mixtures thereof, in particular titanium dioxide (amorphous or rutile and / or anatase). Type crystalline), zinc oxide and mixtures thereof. Inorganic UV-screening agent is particularly preferably TiO _2.

  These metal oxides may be in the form of particles having an average basic particle size generally less than 200 nm. Advantageously, the metal oxide particles used have an average basic particle size of 0.15 μm or less.

  These metal oxides may also be in the form of layers having an average thickness of generally less than 0.2 μm, preferably multilayers.

  The inorganic UV screening agent according to the present invention preferably has an average basic particle size of more than 5 nm and less than 200 nm. According to one particularly preferred embodiment of the invention, this particle size is preferably in the range of 10 nm to 150 nm.

  According to one embodiment of the present invention, the inorganic UV screening agent may be a nano pigment based on titanium oxide.

  The inorganic UV screening agent may or may not be coated.

  Coated inorganic UV screening agents include, for example, compounds described in Cosmetics & Toiletries, February 1990, 105, 53-64, such as amino acids, beeswax, fatty acids, fatty alcohols, anionic surfactants, lecithins , Fatty acid sodium salt, potassium salt, zinc salt, iron salt or aluminum salt, metal alkoxide (titanium or aluminum alkoxide), polyethylene, silicone, protein (collagen, elastin), alkanolamine, silicon oxide, metal oxide, Or a pigment that has undergone a surface treatment of one or more chemical, electrical, mechanochemical and / or mechanical properties, such as sodium hexametaphosphate.

  As is known, silicones are linear or cyclic, branched or crosslinked organosilicon polymers or oligomers of various molecular weights obtained by polymerization and / or polycondensation of appropriately functionalized silanes; From repetition of a main unit in which silicon atoms are linked together through oxygen atoms (siloxane bond) and an optionally substituted hydrocarbon-based group directly bonded to the silicon atom through a carbon atom Essentially composed.

  The term “silicone” also includes the silanes required for their preparation, especially alkyl silanes.

  The silicone used for coating the pigments suitable for the present invention is preferably selected from the group containing alkylsilanes, polydialkylsiloxanes and polyalkylhydrogenosiloxanes. Even more preferentially, the silicone is selected from the group containing octyltrimethylsilane, polydimethylsiloxane and polymethylhydrogenosiloxane.

  Needless to say, the metal oxide pigment may be treated with another surface agent, particularly cerium oxide, alumina, silica, aluminum compound, or silicon compound, or a mixture thereof, before the silicone treatment.

Coated pigments include, among others:
-Titanium oxide coated with silica, e.g. Ikeda product Sunveil,
-Titanium oxide coated with silica and iron oxide, e.g. Ikeda product Sunveil F,
-Titanium oxide coated with silica and alumina, e.g. Tayca's products Microtitanium Dioxide MT 500 SA and Microtitanium Dioxide MT 100 SA, and Tioxide's Tioveil,
-Titanium oxide coated with alumina, e.g. Ishihara products Tipaque TTO-55 (B) and Tipaque TTO-55 (A) and Kemira UVT14 / 4,
-Titanium oxide coated with alumina and aluminum stearate, e.g. Tayca products Microtitanium Dioxide MT100T, MT100TX, MT100Z and MT-01, Uniqema products Solaveil CT-10W and Solaveil CT100, and Merck products Eusolex T -AVO,
-Titanium oxide coated with silica, alumina and alginic acid, for example the product MT-100AQ from Tayca,
-Titanium oxide coated with alumina and aluminum laurate, for example the product Microtitanium Dioxide MT100S from Tayca,
-Titanium oxide coated with iron oxide and iron stearate, e.g. Tayca product Microtitanium Dioxide MT100F,
-Titanium oxide coated with zinc oxide and zinc stearate, for example product BR351 from Tayca,
-Titanium oxide coated with silica and alumina and siliconized, such as Tayca's products Microtitanium Dioxide MT600SAS, Microtitanium Dioxide MT500SAS or Microtitanium Dioxide MT100SAS,
-Titanium oxide coated with silica, alumina and aluminum stearate and siliconized, for example the product STT-30-DS from Titan Kogyo
-Silica coated and siliconized titanium oxide, for example Kemira product UV-Titan X 195,
-Titanium oxide coated with alumina and siliconized, for example Ishihara's product Tipaque TTO-55 (S) or Kemira's product UV Titan M262,
-Titanium oxide coated with triethanolamine, e.g. Titan Kogyo product STT-65-S,
-Titanium oxide coated with stearic acid, for example the product Tipaque TTO-55 (C) from Ishihara,
-Titanium oxide coated with sodium hexametaphosphate, e.g. Tayca product Microtitanium Dioxide MT150W,
-TiO ₂ treated with octyltrimethylsilane sold under the trademark T 805 by the company Degussa Silices,
-TiO ₂ treated with polydimethylsiloxane sold by Cardre under the trademark 70250 Cardre UF TiO2SI3,
-Anatase / rutile TiO ₂ treated with polydimethylhydrogensiloxane sold by Color Techniques under the trademark Microtitanium Dioxide USP Grade Hydrophobic
It is.

  Uncoated titanium oxide pigments are, for example, the trademark Microtitanium Dioxide MT 500 B or Microtitanium Dioxide MT 600 B by Tayca, the name P 25 by Degussa, the name Transparent titanium oxide PW by Wackherr and the name Miyoshi Kasei It is sold in UFTR under the name ITS by Tomen and under the name Tioveil AQ by Tioxide.

Uncoated zinc oxide pigments are, for example,
-Products sold under the name Z-Cote by Sunsmart
-What is sold under the name Nanox by Elementis,
-There is one sold by Nanophase Technologies under the name Nanogard WCD2025.

The coated zinc oxide pigment is, for example,
-Sold under the name Zinc Oxide CS-5 by the company Toshibi (ZnO coated with polymethylhydrogenosiloxane),
- by Nanophase Technologies Corporation sold under the name Nanogard Zinc Oxide FN (Finsolv TN, as C ₁₂ ~C ₁₅ 40% dispersion alkyl benzoate),
-Daito sold under the name Daitoopersion Zn-30 and Daitoopersion Zn-50 (cyclopolymethylsiloxane / oxy-containing 30% or 50% of zinc oxide coated with silica and polymethylhydrogenosiloxane) Ethyleneated polydimethylsiloxane dispersion),
-Sold under the name NFD Ultrafine ZnO by Daikin (ZnO coated with a copolymer based on perfluoroalkyl phosphate and perfluoroalkylethyl as a dispersion in cyclopentasiloxane);
-Sold under the name SPD-Z1 by the company Shin-Etsu (ZnO coated with a silicone-grafted acrylic polymer dispersed in cyclodimethylsiloxane),
-Sold under the name Escalol Z100 by the company ISP (ZincO treated with alumina dispersed in an ethylhexyl methoxycinnamate / PVP-hexadecene copolymer / methicone mixture),
-Sold under the name Fuji ZnO-SMS-10 by Fuji Pigment (ZnO coated with silica and polymethylsilsesquioxane),
-Sold under the name Nanox Gel TN by Elementis (ZnO dispersed at a concentration of 55% in C12-C15 alkylbenzoates containing hydroxystearic acid polycondensates)
There is.

The uncoated cerium oxide pigment may be, for example, that sold under the name Colloidal Cerium Oxide by the company Rhone-Poulenc.
Uncoated iron oxide pigments are sold, for example, under the names Nanogard WCD2002 (FE45B), Nanogard Iron FE45BL AQ, Nanogard FE45R AQ and Nanogard WCD2006 (FE45R) by Arnaud or under the name TY-220 by Mitsubishi. .

  Coated iron oxide pigments are sold, for example, under the names Nanogard WCD2008 (FE45B FN), Nanogard WCD2009 (FE45B556), Nanogard FE45BL345 and Nanogard FE45BL by Arnaud or under the name Transparent Iron Oxide by BASF.

  Also, a mixture of metal oxides, in particular a mixture of titanium dioxide and cerium dioxide, for example an equal weight mixture of silica-coated titanium dioxide and cerium dioxide sold under the name Sunveil A by the company Ikeda, and A mixture of titanium dioxide and zinc dioxide coated with alumina, silica and silicone, for example the product M 261 sold by the company Kemira, or a mixture of titanium dioxide and zinc dioxide coated with alumina, silica and glycerol, Mention may be made, for example, of the product M 211 sold by the company Kemira.

  According to the invention, coated or uncoated titanium oxide pigments are particularly preferred.

  Titanium oxide may be in the rutile and / or anatase form and / or in an amorphous or substantially amorphous form.

1) Particulate organic screening agents Particulate organic UV screening agents containing at least one UV radiation absorbing group are in particular oxalanilide, triazine, benzotriazole, vinylamide, cinnamide, benzazole, benzofuran, arylvinylidene-ketones, acrylonitrile amide , An acrylonitrile sulfonamide, an acrylonitrile carbamate, or a phenylenebisbenzoxazinone type insoluble organic UV screening agent.

  Among the oxalanilide-type particulate organic UV screening agents, mention may be made of those corresponding to the following formula:

(Wherein T ₁ , T ₁ ′, T ₂ and T ₂ ′ each independently represents a C _{1 to} C ₈ alkyl group or a C _{1 to} C ₈ alkoxy group). These compounds are described in patent application WO95 / 22959. By way of example, mention may be made of the commercial products Tinuvin® 315 and Tinuvin® 312 sold by the company Ciba-Geigy, each corresponding to the following formula:

  The triazine type particulate organic UV screening agent corresponds to the following general formula:

[Wherein, R ₁ , R ₂ and R ₃ each independently represent a phenyl group, a phenoxy group or a pyrrolo group, and these groups are unsubstituted or each independently represent —OH, C _{1 -18} alkyl, C _1-18 alkoxy, carboxy (C _1-18 alkyl), C _5-8 cycloalkyl, methylbenzylidene camphor,-(CH = CR ') n (CO) -OR ₄ (where R' Represents a hydrogen atom, a cyano group, or a COOR ₄ group, and R ₄ = C ₁ -C ₁₈ alkyl or cinnamyl, and n is 0 or 1). Has a substituent. ]

These compounds are described in WO97 / 03643, GB2286774, EP743309, WO98 / 22447, GB2319523 and EP-A-0790243.
Among others, the following compounds may be mentioned:
-2,4,6-tris (diethyl 4'-aminobenzalmalonate) -s-triazine,
-2,4,6-tris (diisopropyl 4'-aminobenzalmalonate) -s-triazine,
-2,4,6-tris (dimethyl 4'-aminobenzalmalonate) -s-triazine,
-2,4,6-tris (ethyl α-cyano-4-aminocinnamate) -s-triazine.

  Among the triazine type particulate organic UV screening agents that can be used in the present invention, s-triazine insoluble derivatives having a benzotriazole group and / or a benzothiazole group, for example, those described in the application WO98 / 25922 can also be mentioned. .

  Of these compounds, among others, 2,4,6-tris [(3′-benzotriazol-2-yl-2′-hydroxy-5′-methyl) phenylamino] -s-triazine and 2,4,6 Mention may be made of -tris [(3'-benzotriazol-2-yl-2'-hydroxy-5'-tert-octyl) phenylamino] -s-triazine.

  Among the benzotriazole type particulate organic UV screening agents, there can be mentioned, for example, those represented by the following formula (III) described in International Application WO95 / 22959.

Wherein R ₅ represents a hydrogen atom or a C _{1 to} C ₁₈ alkyl group, and R ₆ and R ₇ may be the same or different and are each independently optionally substituted with a phenyl group. be means good C ₁ -C ₁₈ alkyl group.)

  As examples of compounds of formula (III), commercially available products Tinuvin® 328, 320, 234 and 350 from Ciba-Geigy, which correspond respectively to the following formulas:

And the polytriazine type particulate screening agents described in patent FR2861075.

  Of the benzotriazole type particulate organic UV screening agents, the compounds described in patents US5687521, US5373037, and US5362881, and among them, [2,4′-dihydroxy-3- (2H-benzotriazole- 2-yl) -5- (1,1,3,3-tetramethylbutyl) -2'-n-octoxy-5'-benzoyl] diphenylmethane:

(Sold under the name Mixxim® PB30 by Fairmount Chemical).

  Other benzotriazole type particulate organic UV screening agents include methylene bis (hydroxyphenylbenzotriazole) derivatives having the following structure:

Wherein R ₈ and R ₉ may be the same or different and each optionally substituted with one or more groups selected from C ₁ -C ₄ alkyl and C ₅ -C ₁₂ cycloalkyl or aryl, respectively. Represented C ₁ -C ₁₈ alkyl groups). These compounds are known and are described in the applications US5237071, US5166355, GB-A-2303549, DE19726184 and EP-A-893119.

In the above formula (IV), C ₁ ~C ₁₈ alkyl group may be linear or branched, e.g., methyl, ethyl, n- propyl, isopropyl, n- butyl, isobutyl, tert- butyl, tert- Octyl, n-amyl, n-hexyl, n-heptyl, n-octyl, isooctyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, tetradecyl, hexdecyl, or octadecyl, C _{5 to} C ₁₂ A cycloalkyl group is, for example, cyclopentyl, cyclohexyl, or cyclooctyl, and an aryl group is, for example, phenyl or benzyl.
Of the compounds of formula (IV), those having the following structures are particularly preferred.

  Compound (a) with the name 2,2'-methylenebis [6- (2H-benzotriazol-2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol] is in a non-micronized form And sold under the name Mixxim® BB / 100 by Fairmount Chemical, and in micronized form under the name Tinosorb® M by Ciba Specialty Chemicals.

  Compound (c) with the name 2,2'-methylenebis [6- (2H-benzotriazol-2-yl) -4- (methyl) phenol] is named Fairx Chemical by the name Mixxim® BB / 200. Sold in solid form.

Among the vinylamide type particulate organic screening agents, there can be mentioned, for example, compounds of the formula (V) described in the application WO95 / 22959.
T _3- (Y) _r -C (= O) -C (T ₄ ) = C (T ₅ ) -N (T ₆ ) (T ₇ ) (V)
Wherein T ₃ is optionally selected from one, two or three groups selected from OH, C ₁ -C ₁₈ alkyl, C ₁ -C ₈ alkoxy, or —C (═O) —OT ₈ C _{1 to} C ₁₈ , preferably C _{1 to} C ₅ alkyl group or phenyl group, which may be substituted by, T ₈ represents a C _{1 to} C ₁₈ alkyl group, T ₄ , T ₅ , T ₆ and T ₇ each independently represent a C _{1 to} C ₁₈ , preferably a C _{1 to} C ₅ alkyl group, or a hydrogen atom, Y represents a —NH— group or an oxygen atom, and r represents 0 Or 1.

Among these compounds, mention may be made in particular of
4-octylamino-3-penten-2-one,
Ethyl 3-octylamino-2-butenoate,
3-octylamino-1-phenyl-2-buten-1-one, and
3-dodecylamino-1-phenyl-2-buten-1-one.

  Among the cinnamide type particulate organic screening agents, compounds such as those described in the application WO95 / 22959 and corresponding to the following formula can be mentioned.

(Where
R ₁₀ represents a hydrogen atom or a C ₁ -C ₄ alkyl group, preferably methyl or ethyl,
R ₁₁ represents a hydrogen atom or a C ₁ -C ₄ alkyl group, preferably methyl or ethyl,
R ₁₂ is - (CONH) represents an s- phenyl group, s is 0 or 1, phenyl group, OH, C ₁ -C ₁₈ alkyl, C ₁ -C ₈ alkoxy, or -C (= O ) -OR ₁₃ may be substituted with 1, 2 or 3 groups, R ₁₃ is C ₁ -C ₁₈ alkyl, more preferentially R ₁₂ is a phenyl group, It represents a 4-methoxyphenyl group or a phenylaminocarbonyl group. )

  Further, for example, bis [α, β-disubstituted cinnamide] dimers described in Patent US5888481 having the following structure can also be mentioned.

(Where
Ar ₁ and Ar ₂ may be the same or different and each represents a phenyl group, an aromatic heterocycle, a group containing a fused phenyl nucleus, or a group containing a fused aromatic heterocycle, and one or more same or Can have different substituents,
B and D are other than a hydrogen atom, and each independently represents an organic group,
A and C each independently represents an organic group,
E represents a divalent organic group,
Ar ₁ and Ar ₂ both represent a phenyl group having a substituent —OR, R represents a hydrogen atom or an organic group, A and C both represent a cyano group, and B and D both represent C _{1 to} C A compound in which ₃₅ represents an alkyl group or an alkynyl group, and E represents a divalent organic group,
In particular, compounds having the following structure are excluded. )

  Among the benzazole type particulate organic screening agents, those corresponding to one of the following formulas can be mentioned.

[Where
Each symbol Y independently represents an oxygen atom or a sulfur atom or an NR ₁₅ group;
The symbols Z each independently represent a nitrogen atom or a CH group,
The symbols R ₁₄ are each independently a linear or branched C _{1 to} C ₈ alkyl group optionally having an OH group, a halogen atom, or a silicon atom, or a linear or branched C ₁ It represents -C ₈ alkoxy group,
Each numerical value m is independently 0, 1 or 2,
n represents an integer between 1 and 4 (inclusive)
p is equal to 0 or 1,
Each numerical value q is independently equal to 0 or 1,
The symbols R ₁₅ each independently represent a hydrogen atom, a benzyl group, or a linear or branched C _{1 to} C ₈ alkyl group optionally containing a silicon atom,
A represents a group of valence n selected from those having the following formula:

(In the formula, each symbol R ₁₆ independently represents a halogen atom, a linear or branched C _{1 to} C ₄ alkyl group or an alkoxy group, or a hydroxyl group,
R ₁₇ represents a hydrogen atom or a linear or branched C _{1 to} C ₄ alkyl group, and c = 0 to 4, d = 0 to 3, e = 0 or 1, and f = 0 to 2. )]

These compounds are in particular patent DE676103 and
CH350763, Patent US5501850, Patent US5961960, Patent application
EP0669323, patent US5518713, patent US2463264, article J. Am. Chem. Soc., 79, 5706-5708, 1957, article J. Am. Chem. Soc., 82, 609-611, 1960, patent application EP0921126 and patent application It is described in EP0712855.
As examples of preferred compounds of formula (VIII) of the 2-arylbenzazole family,
Mention may be made of 2-benzoxazol-2-yl-4-methylphenol, 2- (1H-benzoimidazol-2-yl) -4-methoxyphenol, or 2-benzothiazol-2-ylphenol, The compounds can be prepared, for example, according to the method described in patent CH350763.

  Examples of preferred compounds of formula (VIII) of the benzimidazolylbenzazole family include 2,2′-bis-benzimidazole, 5,5 ′, 6,6′-tetramethyl-2,2′-bisbenzimidazole, 5'-dimethyl-2,2'-bisbenzimidazole, 6-methoxy-2,2'-bisbenzimidazole, 2- (1H-benzimidazol-2-yl) benzothiazole, 2- (1H-benzimidazole- 2-yl) benzoxazole and N, N′-dimethyl-2,2′-bisbenzimidazole, which can be prepared according to the procedures described in patents US5961960 and US2463264.

  Examples of preferred compounds of formula (VIII) of the phenylenebenzazole family include 1,4-phenylenebis (2-benzoxazole), 1,4-phenylenebis (2-benzimidazole), 1,3-phenylenebis (2 -Benzoxazole), 1,2-phenylenebis (2-benzoxazole), 1,2-phenylenebis (benzimidazole), 1,4-phenylenebis (N-2-ethylhexyl-2-benzimidazole), and 1 , 4-phenylenebis (N-trimethylsilylmethyl-2-benzimidazole), and these compounds are disclosed in patent US2463264 and publication J. Am. Chem. Soc., 82, 609 (1960), and J. Am It can be prepared according to the procedure described in Chem. Soc., 79, 5706-5708 (1957).

As examples of preferred compounds of formula (VIII) of the benzofuranylbenzoxazole family,
2- (2-benzofuranyl) benzoxazole, 2- (benzofuranyl) -5-methylbenzoxazole, and 2- (3-methyl-2-benzofuranyl) benzoxazole, and these compounds are described in patent US5518713. It can be prepared according to the procedure.

  Preferred compounds of formula (IX) include, for example, 2,6-diphenyl-1,7-dihydrobenzo [1,2-d; 4,5-d ′] diimidazole corresponding to the following formula:

Or 2,6-distyryl-1,7-dihydrobenzo [1,2-d; 4,5-d '] diimidazole, or 2,6-di (p-tert-butylstyryl) -1,7-dihydro Mention may be made of benzo [1,2-d; 4,5-d ′] diimidazole, which can be prepared according to the method described in application EP0669323.
Preferred compounds of formula (X) include 5,5′-bis-[(phenyl-2) benzimidazole] having the following formula:

Its preparation is described in J. Chim. Phys., 64, 1602 (1967).

  Among these insoluble UV radiation shielding organic compounds, 2- (1H-benzoimidazol-2-yl) benzoxazole, 6-methoxy-2,2′-bisbenzimidazole, 2- (1H-benzimidazol-2- Yl) benzothiazole, 1,4-phenylenebis (2-benzoxazole), 1,4-phenylenebis (2-benzimidazole), 1,3-phenylenebis (2-benzoxazole), 1,2-phenylenebis (2-Benzoxazole), 1,2-phenylenebis (2-benzimidazole) and 1,4-phenylenebis (N-trimethylsilylmethyl-2-benzimidazole) are very particularly preferred.

  Another family of particulate screening agents is the family of arylvinylene-ketones selected from those corresponding to one of the following formulas (XI) and (XII).

[Where
n = 1 or 2,
A is an aryl group selected from the following formulas (a) to (d) when n = 1 in the formula (XI) or (XII), or n = In the case of 2, it is a group selected from the following formulas (e) to (h).

(Where
The symbols R ₄ each independently contain an OH group, a halogen atom, and optionally a linear or branched C _{1 to} C ₆ alkyl group optionally containing a silicon atom, optionally containing a silicon atom. A straight chain or branched chain C ₁ -C ₆ alkoxy group, which may optionally contain a straight chain or branched chain C ₁ -C ₅ alkoxycarbonyl group, or optionally a silicon atom or an amino acid functional group. It represents a chain or branched chain C ₁ -C ₆ alkyl sulfonamide group.
p represents an integer between 0 and 4 (inclusive)
q represents 0 or 1,
R ₁ represents hydrogen or an OH group,
R ₂ represents hydrogen, optionally a linear or branched C ₁ -C ₆ alkyl group, a cyano group, a C ₁ -C ₆ alkyl sulfonyl group, or a phenyl sulfonyl group optionally containing a silicon atom. ,
R ₃ can form a linear or branched C ₁ -C ₆ alkyl group optionally containing a silicon atom, or a bicycle, optionally with one or two R ₄ Represents a phenyl group optionally substituted by a group,
Alternatively, R ₂ and R ₃ together can be optionally combined with one or more nitrogen, sulfur, and oxygen atoms, provided that R ₂ and R ₃ do not form a camphor nucleus when n = 1. optionally interrupted even if well can contain a different carbonyl, straight a silicon atom or an amino acid functional group which may contain optionally or branched C ₁ -C ₈ alkyl sulfonamido group may be substituted by a monocyclic, form a bicyclic or tricyclic C ₂ -C ₁₀ hydrocarbon-based residue. )]

Examples of insoluble UV radiation shielding compounds of formula (XI) (where n = 1) include the following families:
Styryl ketone (Kao, JP04134042), for example 1- (3,4-dimethoxyphenyl) -4,4-dimethylpent-1-en-3-one:

Benzylidene cineol (E. Mariani et al., 16th IFSCC Congress, New York (1990)), for example 1,3,3-trimethyl-5- (4-methoxybenzylidene) -2-oxabicyclo [2.2.2] octane-6- on:

Benzylidenechromanone (Kao, JP04134043), such as 3- (4-methoxybenzylidene) -2,3,4a, 8a-tetrahydrochromen-4-one:

Benzylidenethiochromanone (Kao, JP04134043), such as 3- (4-methoxybenzylidene) -2,3,4a, 8a-tetrahydrochromene-4-thione:

Benzylidenequinuclidinone (Merck, EP0576974), such as 4-methoxybenzylidene-1-azabicyclo [2.2.2] octane-3-one:

Benzylidenecycloalkanones (Henkel, FR2395023), such as 2- (4-methoxybenzylidene) cyclopentanone and 2- (4-methoxybenzylidene) cyclohexanone:

Benzylidenehydantoin (Ajinomoto, JP01158090), such as 5- (3,4-dimethoxybenzylidene) imidazolidine-2,4-dione:

Benzylideneindanone (Kao, JP04134043), for example 2- (4-methoxybenzylidene) indan-1-one:

Benzylidenetetralone (Kao, JP04134043), for example 2- (4-methoxybenzylidene) -3,4-dihydro-2H-naphthalen-1-one:

Benzylidenefuranone (L'Oreal, EP0390683), such as 4- (4-methoxybenzylidene) -2,2,5,5-tetramethyldihydrofuran-3-one:

Benzylidenebenzofuranone (Kao, JP04134041), for example 2-benzylidenebenzofuran-3-one:

Benzylideneindanediones, such as 2- (3,5-di (tert-butyl) -4-hydroxybenzylidene) indane-1,3-dione:

Benzylidenebenzothiofuranone (Kao, JP04134043), for example 2-benzylidenebenzo [b] thiophen-3-one:

Benzylidene barbiturates, such as 5- (4-methoxybenzylidene) -1,3-dimethylpyrimidine-2,4,6-trione:

Benzylidenepyrazolones such as 4- (4-methoxybenzylidene) -5-methyl-2-phenyl-2,4-dihydropyrazol-3-one:

Benzylideneimidazolones, such as 5- (4-methoxybenzylidene) -2-phenyl-3,5-dihydroimidazol-4-one:

Chalcones such as 1- (2-hydroxy-4-methoxyphenyl) -3-phenylpropenone:

Benzylidenone (shielded tautomeric form of dibenzoylmethane, L'Oreal, FR2506156), such as 3-hydroxy-1- (2-hydroxy-4-methoxyphenyl) -3-phenylpropenone:

  Examples of insoluble UV radiation shielding compounds of formula (XI) (where n = 2) include the following families:

Phenylene bismethylidene norcamphor (Merck, EP0693471), for example
1,4-phenylenebis {3-methylidenebicyclo [2.2.1] heptan-2-one}:

Phenylenebismethylidene camphor (L'Oreal, FR2528420), for example 1,4-phenylenebis {3-methylidene-1,7,7-trimethylbicyclo [2.2.1] heptan-2-one}:

Or 1,3-phenylenebis {3-methylidene-1,7,7-trimethylbicyclo [2.2.1] heptan-2-one}:

Phenylene bismethylidene camphorsulfonamide (L'Oreal, FR2529887), for example
1,4-phenylenebis {3,3'-methylidenecamphor-10,10'-ethylsulfonamide or-(2-ethylhexyl) sulfonamide}:

Phenylene bismethylidene cineole (E. Mariani et al., 16th IFSCC Congress, New York (1990)), such as 1,4-phenylene bis {5-methylidene-3,3-dimethyl-2-oxa-bicyclo [2.2.2] Octane-6-on}:

Phenylenebis (methylideneketotricyclodecane) (Merck, EP0694521), for example 1,4-phenylenebis (octahydro-4,7-methano-6-inden-5-one):

Phenylenebis (alkylene ketone) (Kao, JP04134041), for example 1,4-phenylenebis (4,4-dimethylpent-1-en-3-one):

Phenylenebis (methylidenefuranone) (L'Oreal, FR2638354), for example 1,4-phenylenebis (4-methylidene-2,2,5,5-tetramethyldihydrofuran-3-one):

Phenylenebis (methylidenequinuclidinone) (Merck, EP0714880), for example 1,4-phenylenebis {2-methylidene-1-azabicyclo [2.2.2] octane-3-one}:

Examples of the compound of the formula (XII) include the following families.
-Bisbenzylidenecycloalkanones such as 2,5-dibenzylidenecyclopentanone:

γ-pyrone (Kao, JP04290882), for example 2,6-bis (3,4-dimethoxyphenyl) pyran-4-one:

Another family of particulate screening agents that can be used in the present invention are acrylonitrile amide, sulfonamide, and carbamate derivatives corresponding to the formula:

[Where
X ₂ represents the formula-(C = O) -R ' _3- (C = O)-,
-SO ₂ -R '' ₃ -SO _2- or-(C = O) -O-R '' ₃ -O- (C = O)-represents a divalent group,
Y represents a-(C = O) -R ₄ group or a -SO ₂ R ₅ group,
R ₂ represents a linear or branched C _{1 to} C ₈ alkyl group,
n is 0, 1 or 2,
R ′ ₃ represents a single bond or R ″ ₃ ,
R '' ₃ may have one or more hydroxyl substituents, and may contain one or more heteroatoms selected from an oxygen atom, a nitrogen atom, and a silicon atom in the carbon-based chain. good, represents a divalent straight or branched C ₁ -C ₃₀ alkylene group or C ₃ -C ₃₀ alkenylene group,
R ₄ represents an -OR ₆ group or a -NHR ₆ group,
R ₅ represents a linear or branched C ₁ -C ₃₀ alkyl group, or a phenyl nucleus optionally substituted with a C ₁ -C ₄ alkyl group or an alkoxy group,
R ₆ may have one or more hydroxyl substituents, and may contain one or more heteroatoms selected from an oxygen atom, a nitrogen atom, and a silicon atom in the carbon-based chain. represents a linear or branched C ₁ -C ₃₀ alkyl or C ₃ -C ₃₀ alkenyl group. ]

  In the above formula (XIII), only the isomer in which the cyano substituent is cis to the para-aminophenyl substituent is shown, but this formula shows the trans isomer corresponding to each of the two double bonds. And cyano substituents and para-aminophenyl substituents should be understood to be independently of one another in cis or trans configuration.

Another family of particulate organic screening agents that can be used according to the present invention is constituted by phenylenebis (benzoxazinone) derivatives having the formula:

(式中、
記号R₄は、それぞれ独立に、OH基、ハロゲン原子、任意選択によりケイ素原子を含有してもよい直鎖若しくは分枝鎖C₁〜C₆アルキル基、任意選択によりケイ素原子を含有してもよい直鎖若しくは分枝鎖C₁〜C₆アルコキシ基、直鎖若しくは分枝鎖C₁〜C₅アルコキシカルボニル基、又は任意選択によりケイ素原子若しくはアミノ酸官能基を含有してもよい直鎖若しくは分枝鎖C₁〜C₆アルキルスルホンアミド基を表し、
pは、両端を含む0から4の間の整数を表し、
qは、0又は1を表す。)] [Wherein R represents a divalent aromatic residue selected from the following formulas (e) to (h).

(Where
Each of the symbols R ₄ independently represents an OH group, a halogen atom, a linear or branched C _{1 to} C ₆ alkyl group that may optionally contain a silicon atom, and optionally a silicon atom. good linear or branched C ₁ -C ₆ alkoxy group, a linear or branched C ₁ -C ₅ alkoxycarbonyl group, or which may linear or min containing silicon atoms or amino functional group optionally represents Edakusari C ₁ -C ₆ alkyl sulfonamide group,
p represents an integer between 0 and 4 inclusive
q represents 0 or 1. )]

Examples of UV radiation shielding particulate compounds of formula (XIV) include the following derivatives:
2,2'-p-phenylenebis (3,1-benzoxazin-4-one) which is the product Cyasorb® UV-3638 from Cytec
2,2 '-(4,4'-biphenylene) bis (3,1-benzoxazin-4-one),
2,2 '-(2,6-naphthylene) bis (3,1-benzoxazin-4-one).

Specific families of other particulate organic screening agents include polyvalent metals of sulfonated or carboxylated organic screening agents (e.g., Ca ²⁺ , Zn ²⁺ , Mg ²⁺ , Ba ²⁺ , Al ³⁺ or Zr ⁴⁺ ) salts, for example polyvalent metal salts of sulfonated derivatives of benzylidene camphor such as those described in application FR-A2639347, polyvalent metals of sulfonated derivatives of benzimidazole such as those described in application EP-A-893119 And polyvalent metal salts of cinnamic acid derivatives such as those described in application JP-87166517.

  Mention may also be made of metals or ammonium or substituted ammonium complexes of UV-A and / or UV-B organic screening agents, such as those described in patent applications WO93 / 10753, WO93 / 11095, and WO95 / 05150.

  A triazine type or benzotriazole type particulate organic screening agent may preferably be selected.

[式中、R₈及びR₉は、同一でも異なっていてもよく、それぞれ、C₁〜C₄アルキル、C₅〜C₁₂シクロアルキル、又はアリールから選択される1つ以上の基で置換されていてもよいC₁〜C₁₈アルキル基を表す。]
とりわけ、2,2'-メチレンビス[6-(2H-ベンゾトリアゾール-2-イル)-4-(1,1,3,3-テトラメチルブチル)フェノール]の名称をもつ化合物(a)、又はFairmount Chemical社によってMixxim(登録商標)BB/100の名称で非微細化形態で販売されている、好ましくは、例えば、Ciba Specialty Chemicals社によってTinosorb M(登録商標)の名称で微細化形態で販売されているメチレンビス(ベンゾトリアゾリルテトラメチルブチルフェノール)である。 Among the insoluble benzotriazole screening agents, it is possible to select a methylene bis (hydroxyphenylbenzotriazole) derivative having the following structure more preferentially.

[Wherein R ₈ and R ₉ may be the same or different and each substituted with one or more groups selected from C ₁ -C ₄ alkyl, C ₅ -C ₁₂ cycloalkyl, or aryl. even if represents an C ₁ -C ₁₈ alkyl group. ]
In particular, the compound (a) having the name 2,2′-methylenebis [6- (2H-benzotriazol-2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol], or Fairmount Sold in non-micronized form under the name Mixxim® BB / 100 by the Chemical Company, preferably sold in micronized form under the name Tinosorb M®, for example by the company Ciba Specialty Chemicals Methylenebis (benzotriazolyltetramethylbutylphenol).

The particulate organic screening agent according to the present invention is generally in the form of particles having an average particle size in the range of 5 nm to 5 μm. More preferentially, this average particle size ranges from 5 nm to 2 μm, in particular from 5 nm to 1.5 μm, especially from 10 nm to 1.0 μm.
In general, the average particle size of the particles corresponds to the average diameter of the distribution by number.

  The average particle size of the particles can be determined by any conventional method such as optical methods (quasi-elastic scattering or laser scattering), centrifugation methods, or microscopy visualization methods and image analysis methods.

  The particulate organic screening agent according to the invention is brought into the desired particulate form, in particular by any suitable means such as dry grinding or grinding in a solvent medium, sieving, atomization, refinement or atomization. Can do.

  The particulate organic screening agent according to the invention in micronized form can in particular be a suitable surfactant or at least one hydrophilic block and at least one which can improve the dispersion of the particles in the resulting cosmetic formulation. It can be obtained by a method of grinding an organic UV screening agent in the form of large particles in the presence of an amphiphilic copolymer containing two hydrophobic blocks.

  Examples of methods for refining particulate organic screening agents are described in applications GB-A-2 303 549 and EP-A-893119, which are an integral part of the present specification. The grinding equipment used according to these documents is an air jet mill, ball mill, vibration mill or hammer mill, preferably a mill or impact mill with a high stirring speed, in particular a rotary ball mill, vibration mill, tube mill or rod mill. It may be.

According to this particular method, as a surfactant for grinding the shielding agent, an alkyl polyglucoside of the structure C _n H _{2n + 1} O (C ₆ H ₁₀ O ₅ ) _× H (where n is It is an integer of 8 to 16, and x is an average degree of polymerization of (C ₆ H ₁₀ O ₅ ) and is in the range of 1.4 to 1.6. They, C ₁ -C ₁₂ ester of a compound of structure _{C n H 2n + 1 O (} C 6 H 10 O 5) x H, especially, formic acid, acetic acid, propionic acid, butyric acid, sulfosuccinic acid, citric acid, or tartaric acid the C ₁ -C ₁₂ carboxylic acids and the like, can be selected from esters obtained by reacting with one or more free OH functions on the glucoside (C ₆ H ₁₀ O ₅₎ units.

  The surfactant is generally in micronized form at a concentration ranging from 1% to 50% by weight and more preferentially from 5% to 40% by weight relative to the weight of the insoluble organic screening agent. Used in.

  Amphiphilic copolymers comprising at least one hydrophilic block and at least one hydrophobic block, such as those described in patent application EP1353642, can also be used to improve the dispersibility of particulate organic screening agents in cosmetic carriers. .

  According to a first variant, the spherical composite particles contain a core comprising at least one organic material and / or at least one inorganic material, in which particles of an inorganic UV screening agent are contained. .

  According to this first variant, the particles of the inorganic UV screening agent are generally characterized by an average basic particle size of less than 200 nm. Advantageously, the metal oxide particles used have an average basic particle size of 0.15 μm or less.

Examples of the composite particles corresponding to this modified form include Sunsil TIN 50 and Sunsil TIN 40 products sold by Sunjin Chemical. These spherical composite particles having an average particle size of 2 to 7 μm are formed by encapsulating TiO ₂ in a silica core.

Moreover, the following particles can also be mentioned.
-Spherical composite particles with an average particle size between 4 and 8 μm, containing TiO ₂ and SiO ₂ with the trade name Eospoly TR sold by Creations Couleurs,
-Composite particles containing a matrix of TiO ₂ and styrene / alkyl acrylate copolymers, sold by Creations Couleurs under the name Eospoly UV TR22 HB 50
-Composite particles containing a matrix of TiO _2, ZnO and PMMA sold by Sunjin Chemical under the trade name Sun PMMA-T50.

Among the composite particles A that can be used according to the invention, mention may also be made of spherical composite particles containing TiO ₂ and SiO ₂ with the trade name STM ACS-0050510 supplied by JGC Catalysts and Chemical.

  According to a second variant, the spherical composite particles A contain an inorganic UV screening agent coated with at least one layer of organic and / or inorganic material. According to this second variant, the particles of inorganic UV screening agent are usually characterized by an average basic particle size of between 0.001 and 0.2 μm. Advantageously, the metal oxide particles used have an average basic particle size of between 0.01 and 0.15 μm.

  According to a third variant, the spherical composite particles A were made of an organic and / or inorganic material coated with at least one layer of inorganic UV screening agent bonded to the matrix using a binder. Contains a core.

  According to this third variant, the average thickness of the layer of inorganic UV screening agent is usually between 0.001 and 0.2 μm, preferably between 0.01 and 0.1 μm.

  The spherical composite particles A used according to the invention have a particle size between 0.1 and 30 μm, preferably between 0.1 and 20 μm, even more preferentially between 0.1 and 10 μm.

According to this particular variant, the spherical composite particle A is
i) having an average particle size greater than 0.1 μm but less than 1 μm, more preferentially less than 0.6 μm, even more preferentially less than 0.4 μm, the surface of which is at least one particulate solid UV as described above Spherical particles A ₁ that are at least partially coated with a screening agent, and optionally
ii) 2 μm or more, preferably 3 μm or more, more preferentially more than 4 μm, better still having an average particle size of 5 μm or more, the surface of which is at least one particulate solid UV screening agent as described above Optional spherical particles A ₂ that are at least partially coated with
You may be comprised from.

The surface of the particle A ₁ or A ₂ may be at least partially coated with at least one powdery colorant.

  In particular, the powdery colorant is selected from pigments and pearlescent agents, and mixtures thereof.

The term pigment "Pigment" is insoluble in the physiological medium is intended to color the composition, of white or colored, to be understood as meaning inorganic or organic particles of any shape is there.

  The pigment may be white or colored and may be inorganic and / or organic.

  Among the inorganic pigments that may be mentioned are titanium dioxide, zirconium oxide, or cerium oxide, which may optionally be surface treated, and also zinc oxide, iron oxide (black, yellow, or red), or chromium oxide. , Manganese violet, ultramarine blue, chromium hydrate, and ferric blue, and metal powders such as aluminum powder and copper powder.

Organic pigments are made of the following materials:
Cochineal Carmine,
Organic pigments of azo dyes, anthraquinone dyes, indigoid dyes, xanthene dyes, pyrene dyes, quinoline dyes, triphenylmethane dyes, or fluorane dyes,
And mixtures thereof.

  Among the organic pigments, mention may be made in particular of D & C-approved pigments known under the following names: D & C Blue 4, D & C Brown 1, D & C Green 5, D & C Green 6, D & C Orange 4, D & C Orange 5 , D & C Orange 10, D & C Orange 11, D & C Red 6, D & C Red 7, D & C Red 17, D & C Red 21, D & C Red 22, D & C Red 27, D & C Red 28, D & C Red 30 No., D & C Red 31, D & C Red 33, D & C Red 34, D & C Red 36, D & C Violet 2, D & C Yellow 7, D & C Yellow 8, D & C Yellow 10, D & C Yellow 11, D & C Yellow 11, FD & C Blue 1 No., FD & C Green 3, FD & C Red 40, FD & C Yellow 5, and FD & C Yellow 6.

  The chemicals corresponding to each of the organic colorants listed above are listed in The Cosmetic, Toiletries and Fragrance Association publication "International Cosmetic Ingredient Dictionary and Handbook", 1997, pages 371-386 and 524-528. It has been.

  The composition according to the invention has a pigment content in the range of 0% to 30% by weight relative to the total weight of the composition, preferably 0.5% to 20% by weight relative to the total weight of the composition. Preferentially, it can be contained in a content ranging from 1% to 10% by weight.

The term pearlescent agent “pearlescent agent” should be understood to mean any form of colored particles, which may or may not have an iridescent color, especially certain types of molluscs. Is produced or synthesized in the shell and has a color effect via optical interference.

  Examples of pearlescent agents that may be mentioned are based on pearlescent pigments such as titanium mica coated with iron oxide, mica coated with bismuth oxychloride, titanium mica coated with chromium oxide, and bismuth oxychloride. Pearlescent pigments. These may also be mica particles having at least two continuous layers of metal oxide and / or organic colorant superimposed on the surface.

Pulverulent colorant is a composite particle of the present invention, the ratio by weight of the particles A ₁ or A ₂ / colorant 50:50 90:10, preferably from 50:50 to 80:20, more preferentially Can be used at a ratio of 50:50 to 70:30.

The coating of particles A ₁ or A ₂ can also contain at least one additional lipophilic or hydrophilic organic UV screening agent.

Additional Organic UV Screening Agents Additional organic screening agents include, among others, dibenzoylmethane derivatives; anthranilic acid esters; cinnamic acid derivatives; salicylic acid derivatives; camphor derivatives; benzophenone derivatives; β, β-diphenyl acrylate derivatives; Benzalmalonate derivatives, particularly those listed in patent US5624663; benzimidazole derivatives; imidazolines; p-aminobenzoic acid (PABA) derivatives; in patent applications EP0832642, EP1027883, EP1300137, and DE10162844 Benzoxazole derivatives described; shielding polymers and silicones, such as those described in particular in application WO 93/04665; α-alkylstyrene dimers such as those described in patent application DE19855649; applications EP0967200, DE19746654, DE19755649, EP-A 4,4-diarylbutadiene as described in -1008586, EP1133980, and EP133981; Soluble merocyanine derivatives, such as those described in application WO04 / 006878, WO05 / 058269 and WO06 / 032 741; as well as mixtures thereof.

  Examples of additional organic UV screening agents include those indicated herein below by their INCI names.

Dibenzoylmethane derivatives:
Butylmethoxydibenzoylmethane (sold by DSM Nutritional Products under the trademark Parsol 1789).

Para-aminobenzoic acid derivatives:
PABA,
Ethyl PABA,
Ethyldihydroxypropyl PABA,
Ethylhexyldimethyl PABA (especially sold by ISP under the name Escalol 507),
Glyceryl PABA,
PEG-25PABA (sold by BASF under the name Uvinul P25).

Salicylic acid derivatives:
Homosalate (sold by Rona / EM Industries under the name Eusolex HMS),
Ethylhexyl salicylate (sold under the name Neo Heliopan OS by Haarmann & Reimer),
Dipropylene salicylate (sold by Scher under the name Dipsal),
Salicylic acid TEA (sold under the name Neo Heliopan TS by Haarmann & Reimer).

Cinnamic acid derivatives:
Ethylhexyl methoxycinnamate (especially sold under the trademark Parsol MCX by Hoffmann LaRoche),
Isopropyl methoxycinnamate,
Isoamyl methoxycinnamate (sold under the trademark Neo Heliopan E 1000 by Haarmann & Reimer),
Synoxate,
Methoxycinnamic acid DEA,
Methyl diisopropylcinnamate,
Glyceryl ethyl hexanoate dimethoxycinnamate.

β, β-diphenyl acrylate derivatives:
Octocrylene (especially sold under the trademark Uvinul N539 by BASF),
Etokurylene (especially sold under the trademark Uvinul N35 by BASF).

Benzophenone derivatives:
Benzophenone-1 (sold by BASF under the trademark Uvinul 400),
Benzophenone-2 (sold by BASF under the trademark Uvinul D50),
Benzophenone-3 or oxybenzone (sold by BASF under the trademark Uvinul M40),
Benzophenone-4 (sold by BASF under the trademark Uvinul MS40),
Benzophenone-5,
Benzophenone-6 (sold by Norquay under the trademark Helisorb 11),
Benzophenone-8 (sold by the American Cyanamid company under the trademark Spectra-Sorb UV-24),
Benzophenone-9 (sold by BASF under the trademark Uvinul DS-49),
Benzophenone-12,
N-hexyl 2- (4-diethylamino-2-hydroxybenzoyl) benzoate sold under the trademark Uvinul A + by BASF or its mixture form with octyl methoxycinnamate sold under the trademark Uvinul A + B .

Benzylidene camphor derivatives:
3-benzylidene camphor (manufactured by Chimex under the name Mexoryl SD),
4-methylbenzylidene camphor (sold by Merck under the name Eusolex 6300),
Benzylidene camphor sulfonic acid (manufactured by Chimex under the name Mexoryl SL),
Benzalkonium sulfate (produced by Chimex under the name Mexoryl SO),
Terephthalylidene dicamphorsulfonic acid (manufactured by Chimex under the name Mexoryl SX),
Polyacrylamide methylbenzylidene camphor (manufactured by Chimex under the name Mexoryl SW).

Phenylbenzimidazole derivatives:
Phenylbenzimidazolesulfonic acid (especially sold under the trademark Eusolex 232 by Merck),
Phenyldibenzimidazole tetrasulfonate disodium (sold by Haarmann and Reimer under the trademark Neo Heliopan AP).

Benzotriazole derivatives:
Drometrizole trisiloxane (sold by Rhodia Chimie under the trademark Silatrizole).

Triazine derivatives:
Bis-ethylhexyloxyphenol methoxyphenyl triazine (sold by Ciba Geigy under the trademark Tinosorb S),
Ethylhexyltriazone (especially sold under the trademark Uvinul T150 by BASF),
Diethylhexylbutamide triazone (sold by Sigma3V under the trademark Uvasorb HEB),
2,4,6-tris (diisobutyl 4'-aminobenzalmalonate) -s-triazine,
2,4,6-tris (dineopentyl 4'-aminobenzalmalonate) -s-triazine,
2,4-Bis (dineopentyl 4′-aminobenzalmalonate) -6- (n-butyl 4′-aminobenzoate) -s-triazine.

Anthranilic acid derivatives:
Menthyl anthranilate (sold under the trademark Neo Heliopan MA by Haarmann and Reimer).

Imidazoline derivatives:
Dimethoxybenzylidene dioxoimidazoline ethylhexyl propionate.

Benzalmalonate derivatives:
Dineopentyl 4'-methoxybenzalmalonate,
Polyorganosiloxanes containing benzalmalonate functional groups, such as Polysilicone-15 (sold under the trademark Parsol SLX by the company Hoffmann LaRoche).

4,4-Diarylbutadiene derivatives:
1,1-dicarboxy (2,2′-dimethylpropyl) -4,4-diphenylbutadiene,
And mixtures thereof.

Preferred additional organic blocking agents are selected from:
Ethylhexyl methoxycinnamate,
Homosalate,
Ethylhexyl salicylate,
Octocrylene,
Butylmethoxydibenzoylmethane,
Terephthalylidene dicamphor sulfonic acid,
Disodium phenyldibenzimidazole tetrasulfonate,
Phenylbenzimidazolesulfonic acid,
Benzophenone-3,
N-hexyl 2- (4-diethylamino-2-hydroxybenzoyl) benzoate,
4-methylbenzylidene camphor,
Ethylhexyl triazone,
Bisethylhexyloxyphenol methoxyphenyl triazine,
Diethylhexylbutamide triazone,
2,4,6-tris (dineopentyl 4'-aminobenzalmalonate) -s-triazine,
2,4,6-tris (diisobutyl 4'-aminobenzalmalonate) -s-triazine,
2,4-bis (dineopentyl 4′-aminobenzalmalonate) -6- (n-butyl 4′-aminobenzoate) -s-triazine,
Polysilicone-15,
Drometrizole trisiloxane,
Dineopentyl 4'-methoxybenzalmalonate,
1,1-dicarboxy (2,2′-dimethylpropyl) -4,4-diphenylbutadiene,
And mixtures thereof.

The core of the particle A _{1 and} the core of the particle A ₂ are composed of an inorganic material and / or an organic material.

The inorganic material or organic material may be hollow or porous. The porosity of the material, by the BET ^{method, 0.05m 2 / g~1500m 2 / g} , more preferentially 0.1m ² / g~1000m ² / g, and even more preferentially 0.2 m ^2/500 m ² It may be characterized by a specific surface area of / g.

The inorganic material that can be used in the core of the spherical particles A ₁ or A ₂ according to the invention can be selected from the group formed from glass, silica, and aluminum oxide, and mixtures thereof.

Organic materials that can be used to form the core of the particles A ₁ or A _2, poly (meth) acrylate, polyamide, silicone, polyurethane, polyethylene, polypropylene, polystyrene, polycaprolactam, polysaccharide, polypeptide, polyvinyl derivatives, waxes , Polyesters, and polyethers, and mixtures thereof.

Particle A ₁ is partially coated with at least one layer comprising at least one particulate UV screening agent. Preferably at least 10% of the surface of the particles, preferably at least 50% of the surface of the particles, more preferentially at least 80%, and even better 100% are coated with a solid screening agent.

The thickness of the coating of the particles A _1, some of the factors can be particularly dependent on particle size. Usually the thickness can range from 0.001 to 0.2 μm, preferably from 0.005 to 0.18 μm, more preferentially from 0.01 to 0.150 μm.

If the coating of at least two layers are present on the particles A _1, the thickness and composition of the layers may be the same or different.

The layer (s) of coating may include other materials such as colored pigments and / or additional UV screening agents. These materials may be present in an amount ranging from 1% of the total weight of the material coating the particles A ₁ 50%.

The spherical particles A ₂ have an average particle size of 2 μm or more, preferably 3 μm or more, more preferentially more than 4 μm. This average particle size can be limited to a maximum of 50 μm, preferably a maximum of 30 μm, more preferentially a maximum of 20 μm, and more particularly a maximum of 10 μm.

  The average particle diameter or average diameter is the arithmetic average diameter and can be determined, for example, by calculating the average of the dimensions of about 100 particles selected on the image obtained by scanning electron microscopy.

The spherical particle A ₂ may be hollow or solid, preferably solid.

According to a particularly preferred form, the core of the particles A ₁ is a styrene copolymer, more preferentially a styrene / acrylate copolymer, in particular a styrene / methyl acrylate copolymer, such as the product sold under the trademark Sunspheres by the company Rohm & Haas, And also the products sold under the trademarks SX859 (A) and SX866 (B) by JSR of Japan.

According to a particularly preferred form, the core of the particle A ₂ is
-Polymethacrylate, especially poly (methyl methacrylate), for example the product sold under the trademark MR-7GC by the Soken company in Japan
-Polyamides, for example products sold under the trademark SP-500 by the company Toray or products sold under the trademark Orgasol by the company Arkema,
-Composed of polytetrafluoroethylene, for example the commercial product sold under the name Ceridust 9205F by the company Clariant.

The weight ratio of particles A ₁ / particle A ₂ is 10: 90 to 90: 10, preferably 20: 80 to 80: 20, more preferentially 30: 70-70: can be 30.

The weight ratio of particles A ₁ and particulate UV screening agents, 10: 90 to 90: 10, preferably 20: 80 to 80: 20, more preferentially 30: 70-70: can be 30.

The weight ratio of particles A ₁ / particles A ₂ / particulate UV screening agent is 20: 50: 30-50: 20: 30, preferably 35: 15: 50-15: 35: 50, more preferentially 10 : 20: 70 to 20:10:70, especially 50:20:30 or 35:15:50.

According to a particularly preferred embodiment, the spherical composite particles A are
i) has an average particle size greater than 0.1 μm and less than 1 μm, more preferentially less than 0.6 μm, even more preferentially less than 0.4 μm, the surface of which is at least partially coated with titanium dioxide particles; Spherical particles A ₁ whose particle core is composed of styrene / methyl methacrylate copolymer,
ii) It has an average particle size of 2 μm or more, preferably 3 μm or more, more preferentially more than 4 μm, and even better 5 μm or more, the surface of which is coated with at least titanium dioxide particles, and the core of the particles is poly Spherical particles A ₂ composed of (methyl methacrylate)
including.

According to another particularly preferred form, the spherical hollow composite particles A are
i) having an average particle size greater than 0.1 μm but less than 1 μm, more preferentially less than 0.6 μm, even more preferentially less than 0.4 μm, the surface of which is at least partly of particles of particulate organic UV screening agent Spherical particles A ₁ which are coated and whose core is composed of styrene / methyl methacrylate copolymer,
ii) 2 μm or more, preferably 3 μm or more, more preferentially more than 4 μm, even better has an average particle size of 5 μm or more, the surface of which is coated with at least particles of particulate organic UV screening agent, Spherical particles A ₂ whose core is composed of poly (methyl methacrylate)
including.

  More specifically, the particulate organic UV screening agent is the compound 2,2′-methylenebis [6- (2H-benzotriazol-2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol. Or a solid form is sold under the name Mixxim® BB / 100 by Fairmount Chemical, and a micronized form is sold under the name Tinosorb M® by Ciba Specialty Chemicals. Methylenebisbenzotriazolyltetramethylbutylphenol.

Mechanofusion method The composite particles A according to the present invention can be prepared by subjecting the following to the mechanofusion method:
-Spherical particles A ₁ having an average particle size of more than 0.1 μm and less than 1 μm, more preferentially less than 0.6 μm and even more preferentially less than 0.4 μm
-Optionally, spherical particles A ₂ having an average particle size of 2 μm or more, preferably 3 μm or more, more preferentially more than 4 μm, even better 5 μm or more,
-At least one of the aforementioned solid UV screening agents, and
-Optionally additional UV screening agents and / or powdered colorants as described above.

  The mechano-fusion method consists of a method in which a mechanical force such as a compressive force, a friction force, or a shear force is applied to a plurality of components to bring about fusion of the components.

  The mechano-fusion method can be carried out in a device having a rotating chamber and internal parts attached to the scraper, such as a device sold under the trademark Hosokawa Micron Corporation in Japan.

  Hybridization by mechanofusion is preferably used.

  Hybridization methods were developed in the 1980s. This is a kind of mechanofusion method, and a strong mechanical force is applied to a plurality of particles in order to cause a mechanochemical reaction to form composite particles.

  According to the hybridization method, the mechanical force is generated by a high-speed rotor that can have a diameter in the range of 10 cm to 1 m and can rotate at a speed of 1000 to 10,000 revolutions / minute. The hybridization method can be performed in air or in a dry atmosphere. In fact, the high speed rotation of the rotor can generate a high speed air flow in the vicinity of the rotor. The liquid material can be subjected to a hybridization method in the presence of a solid material.

  The hybridization method can be performed using a hybridization system sold under the trademark Nara Machinery, in which at least two types of particles, typically core-containing particles and microparticles, are dried. Supply to a hybridizer with a high speed rotor with multiple blades in the chamber to disperse the particles in the chamber, where mechanical and thermal energy (compression, friction, and shear) is in a short time, eg 1-10 Minutes, preferably 1-5 minutes. Thereby, one kind of particles (fine particles) is collected on or bonded to another type of particles (that is, particles including a core) to form composite particles. The particles are preferably subjected to electrostatic treatment, for example by vibrating them, to form a “regular mixture” in which one type of particle spreads and covers another type of particle. The hybridization method can be performed using a theta composer sold by Tokuju Corporation.

  The hybridization method can be carried out using a Composi Hybrid or Mechano Hybrid apparatus sold by Nippon Coke.

According to the present invention, the hollow particles A ₁ , the particles A ₂ , the particulate screening agent, optionally a colored pigment and optionally an additional screening agent are optionally introduced into the hybridizer to obtain the composite particles. Form.

  The hybridization method can be performed using a rotor rotating at about 8000 rpm for about 3 minutes.

Inorganic UV Screening Particle B
The inorganic UV screening agents constituting these particles B are generally from metal oxides, preferably titanium oxide, zinc oxide or iron oxide, or mixtures thereof, in particular titanium dioxide, zinc oxide, and mixtures thereof. Selected from. The inorganic UV screening agent is particularly preferably titanium dioxide (TiO ₂ ).

In particular, titanium dioxide (TiO ₂ ) may be rutile and / or anatase and / or amorphous.

  Inorganic UV screening agents, particularly metal oxide particles B, usually preferably have an average basic particle size between 0.07 μm and 0.2 μm.

  According to one particular form of the invention, the particles B may be in powder form.

  The inorganic UV screening agent particles B may be untreated or may be treated with at least one surface treatment agent.

  Non-limiting examples of untreated metal oxides include untreated titanium dioxide, such as products sold by Tayca under the trademark MTY-700B.

  Preferably the hydrophobically modified inorganic UV screening agent particles B are, for example, compounds described in Cosmetics & Toiletries, February 1990, 105, 53-64, such as amino acids, beeswax, fatty acids, fats. Alcohol, anionic surfactant, lecithin, fatty acid sodium salt, potassium salt, zinc salt, iron salt or aluminum salt, metal alkoxide (titanium or aluminum alkoxide), polyethylene, silicone, protein (collagen, elastin), alkanolamine It may be coated by subjecting it to a surface treatment of one or more chemical, electrical, mechanochemical and / or mechanical properties, such as, silicon oxide, metal oxide, or sodium hexametaphosphate.

  As is known, silicones are organosilicon polymers or oligomers of various molecular weights, linear or cyclic, branched or cross-linked structures, obtained by polymerization and / or polycondensation of appropriately functionalized silanes. A substituted hydrocarbon system in which the silicon atoms are linked together via oxygen atoms (siloxane bonds) and optionally optionally bonded directly to the silicon atoms via carbon atoms It consists essentially of repetition with the group. The term “silicone” also includes the silanes required for their preparation, especially alkyl silanes.

Preferably, metal oxide particles coated with dimethicone and at least one surface treatment selected from linear or branched C ₁₂ -C ₁₈ fatty acids, especially stearic acid, are used.

  Hydrophobically modified particles B made of inorganic UV screening agents, especially metal oxides, are also used as other surface treatment agents, especially cerium oxide, alumina, silica, aluminum compounds such as aluminum hydroxide or silicon compounds, or these May be treated with a mixture of

  Non-limiting examples of hydrophobically treated titanium dioxide particles include titanium dioxide treated with dimethicone, such as the product sold under the trademark MTY-700BS by Tayca, silica / alumina / stearic acid or alumina / stearate. Mention may be made of titanium dioxide treated with an acid mixture.

According to a particular form of the invention, the particles B may be in the form of an oily dispersion. The oil present in the oily dispersion of particles of the inorganic UV screening agent is preferably selected from triglycerides such as C ₁₂ -C ₁₅ alkyl benzoates or capryl / capprint triglycerides.

  The oily dispersion of particles B of a hydrophobically modified inorganic UV screening agent can also contain at least one dispersant, for example polyhydroxystearic acid.

In particular, the following oily dispersions of TiO ₂ particles treated with a mixture of stearic acid, polyhydroxystearic acid and alumina are used:
Titanium dioxide (and) C ₁₂ -C ₁₅ alkyl benzoate (and) polyhydroxystearic acid (and) stearic acid (and) alumina, for example the product sold under the trademark Solaveil XT-100 by Croda;
-Titanium dioxide (and) capryl / capric triglyceride (and) polyhydroxystearic acid (and) stearic acid (and) alumina, for example the product sold under the trademark Solaveil XT-300 by Croda.
Preferably, the content of inorganic B screening agent particles B in the composition according to the invention is between 0.1% and 40% by weight, preferably between 0.5% and 30% by weight, relative to the total weight of the composition. More preferentially between 1% and 20% by weight.

The aqueous phase of the composition of the aqueous phase present invention optionally contain other water-soluble or water-miscible organic solvents with water and optionally.

  Aqueous phases suitable for the present invention may include, for example, natural spring water, such as La Roche-Posay water, Vittel water, or Vichy water, or water selected from floral water.

Water-soluble or water-miscible solvents suitable for the present invention, short-chain monoalcohols, for example, C ₁ -C ₄ monoalcohols, such as ethanol or isopropanol; diols or polyols, such as ethylene glycol, 1,2-propylene glycol, 1 , 3-butylene glycol, hexylene glycol, diethylene glycol, dipropylene glycol, 2-ethoxyethanol, diethylene glycol monomethyl ether, triethylene glycol monomethyl ether, glycerol and sorbitol, and mixtures thereof.

  According to preferred embodiments, inter alia, ethanol, propylene glycol, glycerol, and mixtures thereof may be used.

  The water or aqueous phase is in the composition according to the invention 5% to 90%, in particular 5% to 75%, in particular 10% to 70% by weight relative to the total weight of the composition. It can be present in a range of content.

  The water-soluble organic solvent can be present in the composition according to the invention in a content ranging from 1% to 30% by weight, in particular from 2% to 20% by weight, relative to the total weight of the composition.

The composition of the oily phase present invention may also comprise at least one oily phase comprising at least one oil.

  For the purposes of the present invention, the term “oily phase” means a phase comprising at least one oil and all fat-soluble and lipophilic components and fatty substances used in the formulation of the composition of the invention. To be understood.

  The term “oil” is understood to mean any fatty substance that is in liquid form at room temperature (20-25 ° C.) and atmospheric pressure (760 mmHg).

  Oils suitable for the present invention may be volatile or non-volatile.

  Oils suitable for the present invention can be selected from hydrocarbon oils, silicone oils, fluorinated oils, and mixtures thereof.

  The hydrocarbon-based oil suitable for the present invention may be an animal hydrocarbon-based oil, a vegetable hydrocarbon-based oil, a mineral hydrocarbon-based oil, or a synthetic hydrocarbon-based oil.

  Oils suitable for the present invention can advantageously be selected from mineral hydrocarbon oils, vegetable hydrocarbon oils, synthetic hydrocarbon oils, silicone oils, and mixtures thereof.

  For the purposes of the present invention, the term “silicone oil” is understood to mean an oil comprising at least one silicon atom, in particular at least one Si—O group.

  The term “hydrocarbon-based oil” is understood to mean an oil mainly containing hydrogen and carbon atoms.

  The term “fluorinated oil” is understood to mean an oil containing at least one fluorine atom.

  Hydrocarbon oils suitable for the present invention are, for example, in the form of hydroxyl groups, amine groups, amide groups, ester groups, ether groups or acidic groups, in particular in the form of hydroxyl groups, ester groups, ether groups or acidic groups, Oxygen atoms, nitrogen atoms, sulfur atoms, and / or phosphorus atoms can optionally further be included.

  The oily phase generally comprises at least one volatile or non-volatile hydrocarbon-based oil and / or one volatile and / or non-volatile silicone oil in addition to one or more lipophilic UV screening agents. Including.

For the purposes of the present invention, the term “volatile oil” is understood to mean an oil that can evaporate in less than one hour at room temperature and atmospheric pressure when left in contact with the skin or keratin fibers. Is done. The volatile oils of the invention are liquid at room temperature and at room temperature and atmospheric pressure, in particular from 0.13 Pa to 40000 Pa (10 ⁻³ to 300 mmHg), in particular from 1.3 Pa to 13000 Pa (0.01 to 100 mmHg), especially Volatile cosmetic oil having a non-zero vapor pressure in the range of 1.3 Pa to 1300 Pa (0.01 to 10 mmHg).

The term “non-volatile oil” means an oil that remains at room temperature and atmospheric pressure for at least a few hours on the skin or on keratin fibers and in particular has a vapor pressure of less than 10 ⁻³ mmHg (0.13 Pa).

Hydrocarbon oils Non-volatile hydrocarbon oils that can be used in accordance with the present invention can be specifically mentioned as
(i) Hydrocarbon oils of plant origin, such as triglyceride esters, which are generally fatty acid triesters of glycerol, these fatty acids can have various chain lengths from C ₄ to C ₂₄ , these chains are Probably linear or branched, saturated or unsaturated; these oils are specifically wheat germ oil, sunflower oil, grape seed oil, sesame seed oil, corn oil, apricot oil, castor oil, Shea oil, avocado oil, olive oil, soybean oil, sweet almond oil, palm oil, rapeseed oil, cottonseed oil, hazelnut oil, macadamia oil, jojoba oil, alfalfa oil, poppy seed oil, pumpkin oil, mallow oil, blackcurrant oil, Evening primrose oil, millet oil, barley oil, quinoa oil, rye oil, safflower oil, kukui oil, passion flower oil Musk rose oil; or else caprylic / capric acid triglycerides such as those sold by Stearineries Dubois company or those sold under the names Miglyol 810, 812 and 818 by the company Dynamit Nobel;
(ii) synthetic ethers containing 10 to 40 carbon atoms;
(iii) linear or branched hydrocarbons of inorganic or synthetic origin, such as petroleum jelly, polydecene, hydrogenated polyisobutenes such as pearl reames, and squalane, and mixtures thereof;
(iv) Synthetic esters, for example oils of the formula RCOOR ′, wherein R represents a residue of a straight-chain or branched fatty acid containing 1 to 40 carbon atoms and R ′ represents a hydrocarbon chain, in particular Represents a branched hydrocarbon chain containing 1 to 40 carbon atoms, where R + R ′ ≧ 10. ], For example, pure serine oil (cetearyl octoate), isopropyl myristate, isopropyl palmitate, C ₁₂ -C ₁₅ alkyl benzoates, eg products sold by Witco under the trademarks Finsolv TN or Witconol TN, or Evonik Goldschmidt Products sold by Tegosoft TN from 2-ethylphenyl benzoate, such as the commercial products sold by ISP under the name X-Tend 226, isopropyl lanolinate, hexyl laurate, diisopropyl adipate, isononyl isononanoate, Oleyl erucate, 2-ethylhexyl palmitate, isostearyl isostearate, diisopropyl sebacate, for example the product sold under the name `` Dub Dis '' by the company Steininerie Dubois, an octoate ester of alcohol or polyhydric alcohol, a decanoate ester or Ricinol Acid esters such as propylene glycol dioctanoate; hydroxylated esters such as isostearyl lactate or diisostearyl malate; and pentaerythritol esters; citrate esters or tartaric esters such as linear di (C ₁₂ -C ₁₃ alkyl) tartaric acid Esters, such as those sold under the name Cosmacol ETI from Enichem Augusta Industriale, and linear di (C ₁₄ -C ₁₅ alkyl) tartaric acid esters, such as those sold under the name Cosmacol ETL; or acetate esters ;
(v) fatty alcohols that are liquid at room temperature, including branched and / or unsaturated carbon chains having 12 to 26 carbon atoms, such as octyldodecanol, isostearyl alcohol, oleyl alcohol, 2-hexyldecanol, 2-butyloctanol or 2-undecylpentadecanol;
(vi) higher fatty acids such as oleic acid, linoleic acid or linolenic acid;
(vii) carbonates, for example dicaprylyl carbonate, for example the product sold under the name Cetiol CC by the company Cognis;
(viii) Fatty amides such as isopropyl N-lauroyl sarcosinate, such as the product sold under the trademark Eldew SL205 by the company Ajinomoto;
And mixtures thereof.

Particular mention may be made of volatile hydrocarbon oils which can be used according to the invention, hydrocarbon oils having 8 to 16 carbon atoms, in particular branched C _{8 to} C ₁₆ alkanes, such as C of petroleum origin. _{8 to} C ₁₆ isoalkanes (also known as isoparaffins), for example isododecane (also known as 2,2,4,4,6-pentamethylheptane), isodecane or isohexadecane, or WO2007 / 068371 or WO2008 Alkanes (mixtures of different alkanes differentiated by at least one carbon) as described in the patent application from Cognis, described at 155059. These alkanes, fatty alcohols obtained from coconut oil or palm oil, the oils sold under the trademark Isopar or Permethyl, branched C ₈ -C ₁₆ esters, isohexyl neopentanoate, and obtained from these mixtures.

  Other volatile hydrocarbon-based oils may also be used, such as petroleum distillates, especially those sold under the name Shell Solt by the company Shell. According to one embodiment, the volatile solvent is selected from volatile hydrocarbonaceous oils having from 8 to 16 carbon atoms, and mixtures thereof.

Silicone oils Non-volatile silicone oils are particularly non-volatile polydimethylsiloxanes (PDMS), alkyl groups or alkoxy groups that are pendant and / or at the end of the silicone chain (these groups are each 2 to 24 carbon atoms). Containing polydimethylsiloxane, or phenyl silicone, such as phenyltrimethicone, phenyldimethicone, phenyl (trimethylsiloxy) diphenylsiloxane, diphenyldimethicone, diphenyl (methyldiphenyl) trisiloxane, or (2-phenylethyl) trimethylsiloxy You can choose from silicates.

Examples of volatile silicone oils that may be mentioned are, for example, volatile linear or cyclic silicone oils, in particular those having a viscosity ≦ 8 centistokes (8 × 10 ⁻⁶ m ² / s), in particular two These silicones optionally contain alkyl or alkoxy groups having 1 to 10 carbon atoms. Examples of volatile silicone oils that can be used in the present invention include octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, heptamethylhexyltrisiloxane, heptamethyloctyltrisiloxane, hexamethyl. Disiloxane, octamethyltrisiloxane, decamethyltetrasiloxane, dodecamethylpentasiloxane, and mixtures thereof.

(式中、Rは、2個から4個の炭素原子を含むアルキル基を表し、その1個以上の水素原子は、フッ素原子又は塩素原子で置き換えられ得る。) Mention may also be made of volatile linear alkyltrisiloxane oils of the general formula (I).

(Wherein R represents an alkyl group containing 2 to 4 carbon atoms, one or more hydrogen atoms of which can be replaced by fluorine atoms or chlorine atoms.)

Among the oils of general formula (I), the following may be mentioned:
3-butyl-1,1,1,3,5,5,5-heptamethyltrisiloxane,
3-propyl-1,1,1,3,5,5,5-heptamethyltrisiloxane, and
3-ethyl-1,1,1,3,5,5,5-heptamethyltrisiloxane, which is an oil of formula (I) in which R is a butyl group, a propyl group, or an ethyl group, respectively. It corresponds to.

Fluorinated oils Volatile fluorinated oils such as nonafluoromethoxybutane, decafluoropentane, tetradecafluorohexane, dodecafluoropentane, and mixtures thereof can also be used.

  The oily phase (excluding the lipophilic organic UV screening agent) ranges from 3% to 60%, preferably from 5% to 30% by weight relative to the total weight of the composition.

  The oily phase according to the invention can further comprise other fatty substances mixed with or dissolved in the oil.

Other fatty substances that may be present in the oily phase can be, for example:
-Fatty acids selected from fatty acids containing 8 to 30 carbon atoms, such as stearic acid, lauric acid, palmitic acid, and oleic acid;
-Waxes selected from lanolin, beeswax, carnauba wax, or candelilla wax, paraffin wax, montan wax, microcrystalline wax, ceresin or ozokerite, or synthetic waxes such as polyethylene wax or Fischer-Tropsch wax;
-A gum selected from silicone gum (dimethiconol);
-Pasty compounds such as polymeric or non-polymeric silicone compounds, esters of glycerol oligomers, arachidyl propionate, fatty acid triglycerides and derivatives thereof;
-As well as mixtures of these.

Gallenic Form The composition according to the invention can be prepared according to techniques well known to those skilled in the art.

  These may be in the form of aqueous lotions or aqueous gels, or contain at least one fatty phase in addition to the aqueous phase and are in the form of simple or complex emulsions (O / W, W / O, O / W / O or W / O / W), for example in the form of an emulsion, cream or cream gel. This may optionally be packaged as an aerosol and may be in the form of a spray.

  The composition according to the invention is preferably in the form of an oil-in-water or water-in-oil emulsion, more preferentially a water-in-oil emulsion.

  The emulsification processes that can be used are of the paddle or impeller, rotor-stator and high pressure homogenizer (HPH) type.

  In order to obtain stable emulsions with low emulsifying compounds (oil / emulsifier ratio> 25), it is possible to make a dispersion in the concentrated phase and then dilute the dispersion with the remaining aqueous phase is there.

  It is also possible to obtain a stable dispersion with a drop diameter of 100 nm which can be accommodated via HPH (between 50 and 800 bar).

  Emulsions generally contain at least one emulsifier selected from amphoteric, anionic, cationic or nonionic emulsifiers used alone or as a mixture. This emulsifier is appropriately selected depending on the emulsion to be obtained (W / O or O / W). Emulsions can also contain other types of stabilizers, such as fillers, or gelling or thickening polymers.

  For O / W emulsions, examples of emulsifiers that may be mentioned include nonionic emulsifiers such as oxyalkylenated (especially polyoxyethylenated) esters of fatty acids and glycerol; fatty acid and oxyalkylenated esters of sorbitan; fatty acids Oxyalkylenated (oxyethylenated and / or oxypropylenated) esters, such as PEG-100 stearate / glyceryl stearate mixture sold under the name Arlacel 165 by the company ICI; oxyalkylenated fatty alcohols ( Oxyethylenated and / or oxypropylenated) ethers; sugar esters such as sucrose stearate; or fatty alcohols and sugar ethers, especially alkylpolyglucosides (APG) such as Plantaren 2000 and Plantaren 1200 by Henkel respectively Decyl glucoside and lauryl glucoside sold under the name, such as cetostearyl glucoside sold under the name Montanov 68 by SEPPIC, Tegocare CG90 by Goldschmidt and Emulgade KE3302 by Henkel (Optionally as a mixture with cetostearyl alcohol), and also of a mixture of arachidyl alcohol, behenyl alcohol, and arachidyl glucoside, for example sold under the name Montanov 202 by the company SEPPIC The form of arachidyl glucoside is mentioned. According to one particular embodiment of the invention, the mixture of alkylpolyglucoside as defined above and the corresponding fatty alcohol is in the form of a self-emulsifying composition as described, for example, in document WO-A-92 / 06778 It may be.

  Among other emulsion stabilizers, isophthalic acid or sulfoisophthalic acid polymers, especially phthalate / sulfoisophthalate / glycol copolymers, such as those sold by Eastman under the name Eastman AQ Polymer (AQ35S, AQ38S, AQ55S and AQ48 Ultra) Diethylene glycol / phthalate / isophthalate / 1,4-cyclohexanedimethanol copolymer (INCI name: Polyester-5) can also be used.

  Among the other emulsion stabilizers, mention may also be made of hydrophobically modified 2-acrylamido-2-methylpropanesulfonic acid polymers, for example those described in patent application EP1069142.

  When it is an emulsion, the aqueous phase of this emulsion is a non-ionic prepared according to known methods (Bangham, Standish, and Watkins, J. Mol. Biol., 13, 238 (1965), FR2315991, and FR2416008). Sex vesicle dispersions can be included.

  Examples of the emulsifying surfactant that can be used for the preparation of the W / O emulsion include an emulsifying surfactant having an HLB of 5 or less at 25 ° C.

  The term HLB (Hydrophilic Lipophilic Balance) is well known to those skilled in the art and represents the hydrophilic-lipophilic balance of the surfactant.

  The surfactant HLB used according to the invention is the HLB by Griffin as defined in the publication J. Soc. Cosm. Chem. 1954 (Vol. 5), pages 249-256.

  Non-limiting examples of surfactants with an HLB of 5 or less are listed in the chapter titled “HLB Index” in a publication titled McCutcheon's Emulsifiers & Detergents, 1998 International Edition, MC Publishing Company, among others. Has been.

  Examples of W / O emulsifying surfactants that may be mentioned are sorbitan, glycerol, polyols or sugar alkyl esters or ethers; silicone surfactants, eg dimethicone copolyols, eg sold under the name DC5225C by the company Dow Corning Mixtures of cyclomethicone and dimethicone copolyols, and alkyl dimethicone copolyols such as lauryl methicone copolyol sold under the name Dow Corning 5200 Formulation Aid by the company Dow Corning; cetyl dimethicone copolyols such as , A product sold under the name Abil EM 90R by Goldschmidt, and a mixture of cetyl dimethicone copolyol, polyglyceryl isostearate (4 mol) and hexyl laurate, sold under the name Abil WE O9 by Goldschmidt. Can be mentioned. One or more co-emulsifiers may also be added to them, and the co-emulsifier may advantageously be selected from the group consisting of polyol alkyl esters.

  Non-silicone emulsifiers are preferred, especially sorbitan, glycerol, polyols or alkyl esters or ethers of sugars.

  Among the alkyl esters of polyols that may be mentioned in particular are polyethylene glycol esters, such as PEG-30 dipolyhydroxystearate, such as the product sold under the name Arlacel P135 by the company ICI.

  Examples of esters of glycerol and / or sorbitan that may be mentioned are polyglyceryl isostearate, for example the product sold under the name Isolan GI 34 by the company Goldschmidt, sorbitan isostearate, for example sold under the name Arlacel 987 by the company ICI And sorbitan glyceryl isostearate, such as the product sold under the name Arlacel 986 by the company ICI, and mixtures thereof.

  According to one particularly preferred form of the invention, the composition is in the form of a water-in-oil emulsion.

Additives Compositions according to the present invention are in particular organic solvents, ionic or nonionic hydrophilic or lipophilic thickeners, softeners, moisturizers, opacifiers, stabilizers, emollients, silicones, antiseptics. Foaming agent, fragrance, preservative, anionic, cationic, nonionic, zwitterionic or amphoteric surfactant, filler, polymer, propellant, basifying or acidifying agent, or Standard cosmetic adjuvants selected from any other ingredients commonly used in the cosmetic and / or dermatological field can also be included.

  Among the organic solvents, mention may be made of lower alcohols and polyols. The polyol can be selected from glycols and glycol ethers such as ethylene glycol, propylene glycol, butylene glycol, dipropylene glycol, or diethylene glycol.

Hydrophilic thickeners that may be mentioned include carboxyvinyl polymers such as, Carbopol products (carbomers) and Pemulen products (acrylate / C ₁₀ -C ₃₀ alkyl acrylate copolymer); polyacrylamides, for example Sepigel 305 (CTFA name: Poly Cross-linked copolymer sold by SEPPIC under the name Acrylamide / C ₁₃ -C ₁₄ Isoparaffin / Laureth 7) or Simugel 600 (CTFA name: Acrylamide / acryloyldimethyltaurine sodium copolymer / isohexadecane / polysorbate 80); optionally cross-linked And / or optionally neutralized 2-acrylamido-2-methylpropanesulfonic acid polymers and copolymers, such as poly (s) sold by Clariant under the trademark Hostacerin AMPS (CTFA name: polyacryloyldimethyltaurate ammonium) 2-acrylamido-2-methyl Propanesulfonic acid) or Simulgel 800 (CTFA name: sodium polyacryloyldimethyltaurate / polysorbate 80 / sorbitan oleate) sold by the company SEPPIC: copolymer of 2-acrylamido-2-methylpropanesulfonic acid and hydroxyethyl acrylate, Examples include Simulgel NS and Sepinov EMT 10 sold by the company SEPPIC; cellulose derivatives such as hydroxyethylcellulose; polysaccharides, especially gums such as xanthan gum; and mixtures thereof.

Lipophilic thickeners that may be mentioned, synthetic polymers, such as poly sold by Landec Corporation under the name Intelimer IPA 13-1 and Intelimer IPA 13-6 (C ₁₀ ~C ₃₀ alkyl acrylate) and the like, Alternatively, modified clays such as hectorite and derivatives thereof, for example, products sold under the name Bentone, can be mentioned.

  The composition according to the invention may also further comprise additional cosmetic and dermatological active agents.

Among the active agents, the following can be mentioned:
-Vitamins (A, C, E, K, PP, etc.) and their derivatives or precursors alone or as a mixture,
- Antioxidant,
-Glee radical scavenger,
-Anti-glycation agents,
-Sedatives,
-NO synthase inhibitors,
-Agents that stimulate the synthesis of dermal or epidermal macromolecules and / or prevent their degradation,
-Agents that stimulate fibroblast proliferation,
-Agents that stimulate keratinocyte proliferation,
-Muscle relaxants,
-Tightening agent,
-Matting agent,
-Keratolytic agents,
-Desquamating agent,
A humectant, for example a polyol such as glycerol, butylene glycol or propylene glycol,
-Anti-inflammatory agents,
-Agents that affect cellular energy metabolism,
-Insect repellent,
-Substance P antagonist or CGRP antagonist,
-Agents for anti-hair loss and / or hair regeneration,
-Antidepressants,
-Additional inorganic and organic UV screening agents, such as those mentioned above.

  Of course, those skilled in the art will recognize that the optional additional compounds described above and the advantageous properties inherent to the composition according to the invention are not adversely affected or substantially not affected by the envisaged addition. You will choose the amount carefully.

  One skilled in the art will select the active agent (s) according to the desired effect on the skin, hair, eyelashes, eyebrows, or nails.

  The cosmetic compositions according to the invention find use in many treatments, in particular in the skin, lip and hair cosmetic treatments, including the scalp.

  Another subject of the present invention is in the manufacture of products for the cosmetic treatment of skin, lips, nails, hair, eyelashes, eyebrows and / or scalp, in particular care products, sunscreen products and makeup products. Using a defined composition of the invention.

  The cosmetic composition according to the present invention can be used, for example, as a makeup product.

  The cosmetic composition according to the invention is used as a facial and / or bodily care product and / or sunscreen protection product of liquid to semi-liquid consistency, such as, for example, emulsions, more or less rich creams, cream-gels and pastes. Can be used. These may optionally be packaged in an aerosol form and may be in the form of a mousse or spray.

  The composition according to the invention in the form of a vaporizable liquid lotion according to the invention is applied to the skin or hair in the form of fine particles using a pressure device. The apparatus according to the present invention is well known to those skilled in the art and includes a non-aerosol type pump or “atomizer”, an aerosol container containing a propellant, and an aerosol pump using compressed air as a propellant. These devices are described in patents US4077441 and US4850517.

  Compositions packaged as aerosols in accordance with the present invention are generally conventional propellants such as hydrofluorinated compounds, dichlorodifluoromethane, difluoroethane, dimethyl ether, isobutane, n-butane, propane, or trichlorofluoromethane, etc. including. They are preferably present in an amount ranging from 15% to 50% by weight relative to the total weight of the composition.

  The following examples serve to illustrate the invention.

(Examples 1 to 4) Preparation of composite pigments by mechanofusion hybridization method The components shown in Table 1 were mixed with a hybridizer (Nara Machinery Co., Ltd., Japan) equipped with a high-speed rotor having a plurality of blades in a chamber under dry conditions. (Sold by the manufacturer) and subjected to hybridization. As a result, the composite pigments of Examples 1 and 2 could be obtained.

  In each of Examples 1 and 2, the components shown in Table 1 were mixed in a plastic bag at the weight ratio shown in the same table and shaken for several minutes. The mixture is then placed in a hybridizer and the rotor is rotated at 8000 rpm (linear speed 100 m / s) for 3 minutes to obtain the composite pigments of Examples 1 and 2.

(1) スチレン/アクリレートコポリマー：Rohm and Haas社によって販売されているSunspheres
(2) PMMA：Soken社によって販売されているMR-7GC
(3) TiO₂：Tayca社によって販売されているMT-100 TV
(4) Tinosorb-M：BASF社によって販売されているメチレンビスベンゾトリアゾリルテトラメチルブチルフェノール

(1) Styrene / acrylate copolymers: Sunspheres sold by Rohm and Haas
(2) PMMA: MR-7GC sold by Soken
(3) TiO ₂ : MT-100 TV sold by Tayca
(4) Tinosorb-M: Methylenebisbenzotriazolyltetramethylbutylphenol sold by BASF

(Examples 5-7) Water / oil emulsion for sunscreen The following compositions 5-7 were prepared. Each component is shown as a weight percent of active material relative to the total weight of the composition.

Emulsion preparation method:
The oily phase A ₁ is prepared by mixing the starting materials at 80-85 ° C. with mechanical stirring. After A ₁ is cooled to 60-65 ° C., Phase A ₂ and Phase A ₃ are added. The aqueous phase (B ₁ and B ₂ ) is prepared by mixing the starting materials at room temperature with mechanical stirring. The resulting solution is macroscopically homogeneous. The emulsion is prepared by slowly adding the aqueous phase to the oily phase with stirring using a Moritz type homogenizer at a stirring speed of 4500 rpm for 10 minutes. Add oily phase C to the resulting emulsion with gentle stirring, then add phase D and phase E. The resulting emulsion is cooled to room temperature with slow stirring. This is characterized by droplets having a particle size between 1 μm and 10 μm.

These compositions were evaluated according to the following properties.
-Shielding effect, and
-Sensation when applied to the skin.

Examples 5 to 7 were compared to TiO ₂ with an identical content of 14%.

In vitro protocol for assessing shielding effectiveness
In vitro SPF
The sun protection factor (SPF) is determined according to the in vitro method described by BL Diffey in J. Soc. Cosmet. Chem. 40, 127-133 (1989). The measurement was performed using a UV-1000S spectrophotometer manufactured by Labsphere. Each composition is applied to the PMMA blank in the form of a uniform and uniform deposit at a rate of 1 mg / cm ² .

in vitro PPD index
To measure the UV-A protection index, the PPD (persistent deposition blackening) method, which measures the color of the skin observed 2-4 hours after exposing the skin to UV-A, is particularly recommended and used. ing. This method has been adopted by the Japan Cosmetic Industry Association (JCIA) since 1996 as the official test procedure for UV-A labeling of products, and is often used in testing institutions in Europe and the United States. (Japan Cosmetic Industry Association Technical Information “Standards for Measuring UVA Prevention Effects”, issued on November 21, 1995, entered into force on January 1, 1966).

The UVA _PPD Solar Protection Index (UVA _PPD PF) is the UV-A dose (MPPDp) required to reach the pigmentation threshold when using a UV screening agent, and the pigmentation threshold when no UV screening agent is present. Mathematically represented by the ratio to the UV-A dose (MPPDnp) required to reach

The measurement was performed according to an in vitro test using a Labsphere UV-2000S spectrophotometer. Each composition is applied to the PMMA blank in the form of a uniform and even deposit at a rate of 1 mg / cm ² .

Protocol for assessing sensory effects after application to the skin The sensory effect after applying the formulation to the skin is applied to the forearm at a ratio of 2 mg / cm ² and the drying time is 2 minutes. And then assessing the frictional force felt between the finger and the surface of its forearm.

result

These results show that the combination of composite particles A and composite particles B according to the invention in an aqueous medium is considerably higher compared to compositions containing each type of shielding particles individually with the same TiO ₂ content It shows that it is possible to obtain a photoprotective composition exhibiting efficacy and good cosmetic quality.

Claims (20)

In a medium acceptable as a cosmetic,
a) at least one aqueous phase, and
b) Spherical shape having an average particle size between 0.1 and 30 μm, comprising a core composed of at least one particulate UV screening agent and at least one inorganic material and / or at least one organic material Composite particles A in form, and
c) Single particle B of inorganic UV screening agent with average basic particle size greater than 0.07μm
A composition containing at least   The composition according to claim 1, wherein the composite particle A comprises a core comprising at least one organic material and / or at least one inorganic material, wherein particles of a particulate UV screening agent are contained therein.   Spherical composite particle A comprises a core made of an organic and / or inorganic material coated with at least one layer of particulate UV screening agent that may be bonded to the matrix using a binder. 2. The composition according to 1.   The composition according to claim 1, wherein the composite particles A comprise a particulate UV screening agent coated with at least one layer of an organic material and / or an inorganic material.   The content of the composite particles A in the composition according to the invention is from 1% to 70% by weight, preferably from 1.5% to 50% by weight, preferably from 2% to 40% by weight, based on the total weight of the composition The composition according to any one of claims 1 to 4, which is in the range of   The composition according to any one of claims 1 to 5, wherein the inorganic material of the core of the spherical composite particles A is selected from the group formed from glass, silica, aluminum oxide, and mixtures thereof.   The material of the core of the spherical composite particles A is poly (meth) acrylate, polyamide, silicone, polyurethane, polyethylene, polypropylene, polystyrene, polycaprolactam, polysaccharide, polytetrafluoroethylene, polypeptide, polyvinyl derivative, wax, polyester, and 6. A composition according to any one of claims 1 to 5, selected from the group formed from polyethers, as well as mixtures thereof. The core of spherical composite particle A
-SiO ₂ ,
-Poly (methyl methacrylate),
-Copolymers of styrene and C1 / C5 alkyl (meth) acrylate derivatives,
-Polyamide,
8. Composition according to claim 6 or 7, comprising a material or a mixture of materials selected from polytetrafluoroethylene. The particulate UV screening agent is inorganic and is a metal oxide in coated or uncoated form, in particular titanium oxide, zinc oxide or iron oxide, and mixtures thereof, in particular rutile, anatase or amorphous mODE selected from titanium dioxide (TiO _2), a composition according to any one of claims 1 to 8.   The particulate UV screening agent is an organic screening agent, and oxalanilide, triazine, benzotriazole, vinylamide, cinnamide, benzazole, benzofuran, arylvinylidene-ketone, acrylonitrileamide, acrylonitrilesulfonamide, acrylonitrilecarbamate, or phenylenebis 2. From benzoxazinone type insoluble organic UV screening agents, especially methylene bisbenzotriazolyl tetramethylbutylphenol, preferably in micronized form methylenebisbenzotriazolyl tetramethylbutylphenol. 9. The composition according to any one of items 8. Spherical composite particle A
i) having an average particle size greater than 0.1 μm and less than 1 μm, more preferentially less than 0.6 μm, even more preferentially less than 0.4 μm, the surface of which is at least one of the types defined in claims 1 to 10 Spherical particles A ₁ , at least partially coated with a particulate solid UV screening agent,
And optionally depending on the case
ii) having an average particle size of 2 μm or more, preferably 3 μm or more, more preferentially more than 4 μm, better still 5 μm or more, the surface of which is at least one of the types specified in claims 1 to 10 particulate solid spherical particles is at least partially coated with UV screening agent A ₂
The composition according to any one of claims 1, 3 and 5 to 10. Coated particles A ₁ or A ₂ (coating) is also at least one lipophilic or additional hydrophilic organic UV screening agent and / or at least one pulverulent coloring agent, the composition of claim 11 object. Spherical composite particle A
i) has an average particle size greater than 0.1 μm and less than 1 μm, more preferentially less than 0.6 μm, even more preferentially less than 0.4 μm, the surface of which is at least partially coated with titanium dioxide particles; Spherical particles A ₁ whose particle core is composed of styrene / methyl methacrylate copolymer,
ii) It has an average particle size of 2 μm or more, preferably 3 μm or more, more preferentially more than 4 μm, and even better 5 μm or more, the surface of which is coated with at least titanium dioxide particles, and the core of the particles is poly Spherical particles A ₂ composed of (methyl methacrylate)
The composition of Claim 11 or 12 containing this. Spherical composite particle A
i) having an average particle size greater than 0.1 μm but less than 1 μm, more preferentially less than 0.6 μm, even more preferentially less than 0.4 μm, the surface of which is at least partly of particles of particulate organic UV screening agent Spherical particles A ₁ which are coated and whose core is composed of styrene / methyl methacrylate copolymer,
ii) 2 μm or more, preferably 3 μm or more, more preferentially more than 4 μm, even better has an average particle size of 5 μm or more, the surface of which is coated with at least particles of particulate organic UV screening agent, Spherical particles A ₂ whose core is composed of poly (methyl methacrylate)
The composition of Claim 11 or 12 containing this.   15. A composition according to any one of the preceding claims, wherein the inorganic UV screening agent particles B are untreated or treated with at least one surface treatment agent. Particles B of the inorganic UV screening agent are in a coated or uncoated form of metal oxide, in particular titanium oxide, zinc oxide or iron oxide, and mixtures thereof, in particular rutile and / or anatase and / or amorphous It is selected from the form of titanium dioxide (TiO _2), a composition according to any one of claims 1 to 15. Inorganic UV screening agents are in a hydrophobically modified form,
a) at least a first surface treating agent selected from dimethicone and linear or branched C ₁₂ -C ₁₈ fatty acids, especially stearic acid, and
Depending on the option
b) Coated with a second surface treatment selected from cerium oxide, alumina, silica, aluminum based compounds such as aluminum hydroxide, silicon based compounds, or mixtures thereof. The composition according to any one of the above. Inorganic UV-screening agents of the particles B is in the form of an oily dispersion, especially in the form of a dispersion in oil chosen from C ₁₂ -C ₁₅ alkyl benzoate or triglycerides, any one of the claims 1 to 17 The composition according to one item. Particle B of inorganic UV screening agent
-Titanium dioxide treated with dimethicone,
-Titanium dioxide treated with silica / alumina / stearic acid or alumina / stearic acid mixture,
- stearic acid, polyhydroxy stearic acid, and is selected from an oily dispersion of the mixture treated with TiO ₂ particles of alumina, the composition according to any one of claims 1 18.   20. Composition according to any one of the preceding claims, characterized in that it is in the form of an aqueous lotion or an aqueous gel, or in the form of a simple or complex emulsion, in particular in the form of a water-in-oil emulsion.